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THE USE 



OF 



Coal Tar Colors 



IN 



FOOD PRODUCTS 



BY 



HUGO LIEBER 



New York 
H. LIEBER & CO. 

1904 



Two Copies Keceivea 

NOV 14 iyU4 

Couyriaiii entry 

ULASb a XXc. No; 

COPY B. 



Copyright, 1904, by H. Lieber & Co. 






INDEX. 



Preface 5 

What are Coal Tar Colors 7 

Use of Coal Tar Colors 10 

Foreign Pure Food or Sanitary Laws : 

England ., 11 

Austria 12 

Germany 16 

Italy 17 

France 24 

Dinitrosoresorcin 35 

Naphthol Green B 38 

Picric Acid 42 

Saffronsurrogate (Dinitrokresol) 46 

Martius Yellow 67 

Naphthol Yellow S 74 

Brilliant Yellow 78 

Aurantia 81 

Summary 82 

Bismarck Brown 84 

Sudan 1 87 

Metanitrazotin 89 

Paranitrazotin 90 

Orange II 91 

Poncean 4 G. B 95 

Orseille Substitute 96 

Chrysoidin 99 

Diphenylamin Orange 102 



4 COAL TAR COLORS IN FOOD PRODUCTS. 

Metanil Yellow lt)5 

Azarin S 10» 

Fast Brown G 11 ^ 

Wool Black 114 

Naphthol Black P 117 

Congo 120 

Azo Blue 124 

Chrysamin R 126 

Conclusions 129 

Tartrazine 133 

Curcumln 185 

Carmoisin 137 

Ponceau 2 R 139 

Rhodamin B 141 

Naphthol Yellow S 143 

Acid Green S F 144 

Soluble Blue 146 

Naphthol Red S 148 



PREFACE. 

For some time there has been considerable agi- 
tation against the use of Coal Tar Colors in Food 
Products, and almost every State in the Union has 
created what is called a Pure Food Law. 

As I am decidedly of the opinion that the food 
consuming public should be most thoroughly protected 
by proper laws and their strict enforcement, I at the 
same time think that these laws should be created by 
conscientious co-operation of theoretically skilled profes- 
sional men and such men who have a thorough knowl- 
edge of their respective branches of the food indus- 
tries. Thus alone can be created laws which will 
yield a perfect protection to the food consuming public, 
which is the paramount issue, beyond a doubt, but at 
tlie same time laws which will give the honest and 
honorable manufacturer of Food Products a chance to 
supply the needs of the food consuming public. 

"There is a distinction but no opposition between 
theory and practice; each to a certain extent sup- 
poses the other ; theory is dependent on practice, 
practice must have preceded theory." 

— SiE W. Hamilton. 

One of the many arguments forwarded by those 
who advocate the forbidding of the use of any color- 
ing matter in food products is that the food consuming 
public is deceived. The so-called deception is not a 
detrimental one, but just the contrary, for it is a well 
established fact that the digestion is decidedly aided 
by the desire to eat, and the desire to eat again is de- 
cidedly influenced by the appearance of the food pre- 
sented. Almost all the civilized countries of the Uni- 
verse have created Sanitary or Pure Food Laws which 



6 COAL TAR COLORS IN FOOD PRODUCTS. 

are strictly enforced. These laws have been made not 
for the protection of the food industries or for the 
protection of color manufacturers, etc., but for the 
protection of the food consuming public. These 
laws have proven through the course of years and 
through practical experience sound law^s, ' ' and none 
of these laws forbids sweepingly the use of coal tar 
colors^ hut simply limits their use to such colors which 
have been proven beyond a question of a doubt to be 
harmless.^^ I wish to refer to the German, the Aus- 
trian, the French, etc.. Sanitary Laws. 

The time that every housewife could produce her 
own necessities of life has passed. The great masses 
have to be fed by the large growers and manufacturers 
of food products and these food products should neces- 
sarily be prepared so as not to be detrimental to the 
health of the consumer. They must also be prepared 
so as to oflFer a pleasing and appetizing appearance, 
which is again a necessity of a proper food product. 

What we need is a law which will plainly state 
what is forbidden and what is permitted to be used, 
and then have this law enforced to the very letter. 
Hypocritical laws can only be detrimental to the con- 
sumer as well as to the manufacturer. 

This book is not intended to be a scientific treatise 
of coal tar products, as they are well known to every 
chemist. My intention is to write a book which will 
aid the food manufacturers in general to a clearer 
knowledge of these indispensable ingredients and their 
relative advantages and disadvantages. 



WHAT ARE COAL TAR COLORS ? 

As the name indicates, coal tar colors are manu- 
factured from coal tar through certain well known 
processes, which can best be classed as follows : 
Distillation of Coal Tar. 
Manufacture of Aniline. 
Manufacture of the colors. 
The coal tar which is furnished by the coal gas 
manufacturers (by-product) is subject to a dry distil- 
lation. The thereby escaping vapors are fraction- 
ated and condensed into three main groups as 
follows : 

70—180° C.^Crude Benzol. 
180—250° 0.= Crude Naphthalin. 
250 — 400° C.=Crude Anthracene. 
Through further separation and purification of the 
above crude products we obtain what may be termed 
the raw materials for the manufacture of coal tar 
colors. The most important of these are : Naphthalin, 
Phenol, Kresol, Toluol, Benzol, Xylol, * Anthracene, 
etc. 

By subjecting these raw materials to certain treat- 
ments we obtain what is termed intermediate pro- 
ducts. For instance, the raw material benzol, when 
treated with nitric acid, yields the intermediate pro- 
duct **Nitrobenzol," etc. If Mtrobenzol is treated 
with Iron and Hydrochloric Acid we obtain ** Ani- 
line." Aniline when properly treated with Methylic 



8 



COAL TAR COLORS IN FOOD PRODUCTS. 



Alcohol yields ^^Dimethylanilin," which is largely 
used in the production of Methylblue, Methylviolet, 
etc. This shows how the color is produced from the 
intermediate product. Frequently the intermediate 
product is first turned into a new product by certain 
treatment, then this new product is again subject to 
one or more chemical treatments and then yields the 
color proper. 

For instance: By a certain treatment toluol is 
turned into a muriate of amidoazotoluol, which again 
is treated with fuming sulphuric acid. 



ca 




NaO.S 



Av/ 



N=Nv^.s,,S03Na 



\Anh, 

CH3 



This yields the well known color Fast Yellow R. It 
would lead entirely too far to thus describe the many 
combinations and colors formed, nor is that the object 
of this book. 

The colors obtained are divided into various groups 
or classes based upon the relative grouping of the 
atom in the color molecule. 

The main groups are as follows:* 

Nitro Colors. 
Azoxy Colors. 



* G. Schultz & P. Julius. Tabellarische Uebersicht. 



WHAT ARE COAL TAR COLORS ? 9 

Diazoamido Colors. 

Azo Colors. 

Auramin Colors. 

Triphenylmethan — and Diphenylnaphtylme- 
than — Colors. 

Pyronin Colors. 

Acridin Colors. 

Nitroso Colors. 

Oxyketon Colors. 

Indophenyl Colors. 

Oxazin & Thiazin Colors. 

Azine Colors. 

Thiobenzenyl Colors. 

Chinolin Colors. 

Colors of the Indigo group. 

Sulphur Colors, etc. 
The names under which the various colors are 
known, that is, their mercantile names, are volun- 
tarily chosen; frequently they are produced by the 
abbreviation of the scientific names of the respective 
colors which sometimes are of an enormous length, 
for instance: The scientific name for Naphthol Blue B 
is Dimethylamidophenodimethylamido-naphtoxazoni- 
umchloride. 

The names, however, are not to be considered as a 
guarantee of quality, etc., of a color, as frequently 
the same names are used for greatly varying pro- 
ducts, for instance: Phloxin produced by one manu- 
facturer is the potassium salt of tetrabromdichlor- 
fluorescein (C20 H4 CI2 Br4 O5 K2). It is a brownish 
yellow powder, soluble in water producing a cherry 
red solution which has a greenish yellow fluorescence. 



iO COAL TAR COLORS IN FOOD PRODUCTS. 

Phloxin produced by another manufacturer is the 
sodium salt of tetrabromtetrachlorfluorescein (C20 ^2 
CI4 Br 4 O5 Na2). It is a scarlet powder soluble in 
water, producing a bluish red solution which has a 
dark green fluorescence. 



USE OF COAL TAR COLORS, 

The greatest use of coal tar colors is for dyeing 
purposes, and the demand for such purposes is a tre- 
mendous one, as almost all materials are now colored 
and dyed with these colors, for instance: Silk, wool, 
cotton, linen, flax, wood, leather, bones, hair, paper, 
flowers, feathers, soap, inks, etc. But what is of the 
most interest to us is the use of these coal tar pro- 
ducts for coloring of all kinds of food materials, such 
as canned and preserved fruits, syrups, catsups, jams, 
jellies, pastry, candies, wines, cordials, liquors, but- 
ter, etc. 

Whereas most of the coal tar colors are entirely 
harmless, there are certain colors and classes which 
are decidedly detrimental to the human or animal 
system, and whereas it is less essential, yes, nearly 
impossible, for every manufacturer of food products 
to know all those colors which are harmless, it is a 
matter of absolute necessity for him to know those 
colors which are detrimental, and which therefore 
should never be used. 

To show how other countries are protecting the 
food consuming public by forcing the food manufac- 



FOREIGN SANITARY LAWS. 11 

turers to use only such colors which have been proven 
by thorough experiments to be absolutely harmless, I 
will quote (translated) those parts of the sanitary 
laws of the various countries which refer to the use 
of coloring matters in food products, etc. 



ENGLAND. 

Sale of Food and Drugs Act, 1875. 

Description of Offences. 

3. Mixing injurious ingredients with food. — No 
person shall mix, color, stain, or powder, or order or 
permit any other person to mix, color, stain, or pow- 
der, any article of food with any ingi^edient or ma- 
terial so as to render the article injurious to health, 
with intent that the same may be sold in that state, 
and no person shall sell any such article so mixed, 
colored, stained, or powdered, under a penalty in each 
case not exceeding fifty pounds for the first offense; 
every offense, after a conviction for a first offense, 
shall be a misdemeanor, for which the person, on con- 
viction, shall be imprisoned for a period not exceeding 
six months with hard labor. 

Sale of Food and Drugs Act, 1899. 

7. For the purpose of this section an article of food 
shall be deemed to be adulterated or impoverished if 
it has been mixed with any other substance, or if 



12 COAL TAR COLORS IN FOOD PRODUCTS. 

any part of it has been abstracted so as in either 
case to effect injuriously its quality, substance or na- 
ture. 

Provided that an article of food shall not he deemed 
to he adulterated hy reason only of the addition of 
any preservative or coloring matter of such a nature 
and in such quantity as not to render the article in- 
jurious to health (g). 



AUSTRIA. 
Par. 408. 

The use of mineral colors containing copper, 
arsenic, lead and zinc is forbidden in the manufac- 
ture of food products as well as also for painting of 
such materials which come in direct contact with the 
human body. 

The use of starch which has an admixture of above 
mineral colors is also forbidden. 

[On the 1st of March, 1886, the Imperial Austrian 
Government passed a sweeping law forbidding abso- 
lutely the use of all coal tar colors in the manufacture 
of food products. However, the Government was 
soon convinced of its mistake, and the law was re- 
pealed, and a new law substituted for same. Quoting 
both laws herewith (translated)] : 

I. Law of the Minister of State in co-operation 
with the Ministers of Commerce, Justice and Police, 
May 1, 1886, concerning the use of poisonous colors 



FOREIGN SANITARY LAWS. 13 

and preparations detrimental to health in the manu- 
facture of various utensils and the sale of same. 

§ 1 . Forbidden is the use of such colors which con- 
tain metals (iron excepted), such as gamboge, picric 
acid, or aniline in the manufacture of food products, 
including also figures, etc., used for decorating 
purposes and manufactured from tragacanth, starch 
and sugar. 

II. Law of the Minister of the Interior in co-op- 
eration with the Ministers of Commerce and Justice, 
March 1, 1886, concerning the use of aniline or coal 
tar colors in food products. 

The use of colors which have been produced by the 
chemical action upon aniline or other coal tar prod- 
ucts, especially of Rosolsaeure, manufactured by 
various methods, is forbidden in the manufacture of 
food products of all kinds, in accordance with §§ 1 &; 6 
der Vdg. vom Mai, 1866. 

III. Law of the Ministers of the Interior, Fi- 
nance, Commerce and Agriculture of August 10, 
1892, concerning the forbidding of importation of 
wines colored with coal tar colors. 

The importation of wines colored with coal tar 
colors into Austria or Hungary is forbidden. 

V. Law of the Minister of the Interior in co-opera- 
tion with the Ministers of Commerce and Justice, 
September 19, 1895, concerning the use of cei'tain 
coal tar colors for coloring of cakes, pastries, candies, 
and such cordials which are colorless, but which, how- 
ever, through custom, are always colored artificially. 

The law created by the Minister of State in co-op- 



14 COAL TAR COLORS IN FOOD PRODUCTS. 

eration with the Ministers of Commerce, Justice and 
Police, May 1, 1886, and the law af the Minister of 
the Interior in co-operation with the Ministers of 
Commerce and Justice of March i, 1886^ forbidding 
the use of aniline or coal tar colors in the manufac- 
ture of food products^ is hereby repealed and can- 
celled as far as the coloring of cakes, pastries, candies 
and the customary artificially colored cordials is 
concerned. Permitted is the use of Puchsine, Acid 
Fuchsine, Roscellin, Bordeaux, Ponceau, Eosin, Ery- 
throsin, Phloxin, Alizarine Blue, Aniline Blue, Water 
Blue, Induline, Acid Yellow P., Tropseolin 000 
(Orange I), Methylviolett, Malachitgreen, as well as 
also the green colors produced by mixing of the so- 
called Blue and Yellow colors. 

The above mentioned colors permitted for coloring 
of cakes, pastries, candies and cordials can be used 
for such purposes only then, if same have been pur- 
chased in the original packages of the manufacturer. 
The wrapper of the package must contain the state- 
ment that this coal tar color is adapted for use in food 
products. It must also contain the seal or trade mark 
of the manufacturer, as well as also the date and cer- 
tificate of a chemical institute, confirming the purity 
of the product as well as also that it is free of all dele- 
terious admixtures in accordance with chemical an- 
alysis made at least once a year. The manufacturer 
of colors shall at all times be held responsible that the 
colors sold by him with the above mentioned guar- 
antees, seals, trade-marks, etc., shall be free of all 
deleterious adulterations, be same of a metallic or 
organic nature. 



FOREIGN SANITARY LAWS. 15 

VI. Law of the Minister of the Interior in co-opera- 
tion with the Ministers of Commerce and Justice, 
Jan. y2, 1896, concerning additions to the law of 
September 19, 1895, concerning the use of non- 
poisonous coal tar colors. 

Besides the coal tar colors mentioned in the law of 
September 19, 1895, it is also permitted to use Naph- 
thol Yellow (sodium salt of Dinitro-a-Naphthol sul- 
phosaure) in coloring of cakes, pastries, candies and 
cordials. 

The scientific names of the other coal tar colors per- 
mitted to be used are : 

Fuchsine — Rosanilinchlorhydrate. 
Acid Fuchsine or Fuchsine S. or Eubine — Acidu- 
lous sodium or calcium salt of Rosanilindi- 
sulpho acid. 
Kocellin or Roscellin — Sulpho-Oxyazonaphtalin. 
Bordeaux and Ponceau red — Products of the com- 
bination of y^-Naphthol-disulpho acid with 
diazo combinations of Xylol of a higher 
homologene of benzol. 
Eosin — Tetrabrom- Fluorescein. 
Erythrosin — Tetrajod-Fluorescein. 
Phloxin — Tetrabrom-Dichlor-Fluorescein. 
Alizarine Blue — C ^ 7 H ^ NO 4 . 
Aniline Blue — Triphenilrosanilin . 
Water Blue — Sulpho acid of Triphenilrosanilin 

(soluble Blue), 
Induline — Sulpho acid of Azodiphenil Blue and 

its derivatives. 
Acid Yellow R. or Brilliant Yellow R. — Amido 
Sulpho-azobenzol. 



16 COAL TAR COLORS IN FOOD PRODUCTS. 

Tropaeolin 000 or Orange I. — Sulphoazobenzol-a 
Naphthol. 

Methylviolet — Hexa and Penta-Methyl- 
Pararosanilin-chlorhydrate. 
Malachit Green — Tetramethyl - Diamidotri- 
phenyl-Carbinol-chlorhydrate. 



GERMANY. 

Art. III. Law concerning the use of colors detri- 
mental to health in the manufacture of food products 
and utensils — July 5, 1887: 

§ 1. It is forbidden to use colors detrimental to 
health in the manufacture of food products of any de- 
scription which are intended for sale. 

Colors detrimental to health in the sense of this 
law are such colors, coloring materials and composi- 
tions which contain antimony, arsenic, barium, lead, 
cadmium, chrome, copper, quicksilver, uranium, zinc, 
tin, gamboge, corallin and picric acid. 

The Reichskanzler is empowered to specify the 
methods to be used in determining the presence of 
arsenic and tin. 

^ 2. In the manufacture of containers and pack- 
ages intended for food products which are intended 
for sale, or their coverings, colors as stated in § 1 must 
not be used, but in their manufacture may be used 
sulphate of barium, barium lacquers of carbonate of 
barium, chrome oxide, the so-called bronze colors con- 
taining copper, tin [and zinc, tin oxide, cinnabar and 



FOREIGN SANITARY LAWS. 17 

sulphate of tin as well as all colors burned into the 
glass or enamels. This exception shall also extend to 
the exterior coloring of vessels. 

§ 3. For the manufacture of cosmetic materials 
(materials for cleansing or coloring the skin, the hair 
and the mouth) which are intended for sale, the 
materials which are mentioned in § 1 shall not be 
used. 



ITALY. 

Ample and harmful fraud is employed in coloring 
food products with detrimental and mineral sub- 
stances. 

The following salts must be forbidden from this 
use: 

Mixtures of copper (Colorations of azure or 

green), 
lead (Colorations from white to 

yellow). 
* barium (Colorations of chrome 
yellow). 
** ^'arsenic (Colorations of a greenish 

type). 

*' ** mercury (Colorations of red Cinna- 

bar). ' 
*' " antimony (Colorations of yellow or 

red). 
Gamboge (Yellow coloration). 
Eosin and derivatives (Yellow- reddish coloration). 



a ii 



^i 



18 COAL TAR COLORS IN FOOD PRODUCTS. 

Fuchsine and derivatives (Red, Blue and Violet 
colorations). 

The following may be used, however: 

Azure Colors — Indigo, azure of Berlin, ultra- 
marine. 
Bed ^' — Cochineal, carmine, carmined lac, 

oricello, Brazilian lac. 
Yellow '* — Saffron, grain of Avignone, cur- 
cuma, etc. 
Green '* — Mixtures of Indigo or Azure of 

Berlin with yellow colored mat- 
ters. 
Violet ** — Indian wood, mixtures of Indigo 

or azure of Berlin with red of 
vegetable nature. 
Coal tar products: Bordeaux Eed, Chrisoidin, 
Biebrich Red, Naphthol Yellow S. 
Royal Decree No. 55.— Feb. 4th, 1902, Printed in 
the Official Gazetta of the 29th of the same month: 
Humbert 1st by the Grace of God and the Will of the 
Nation king of Italy. 

List of the Harmful Colors in the Alimentary 

Substances. 

Having examined the law for the tutelage of the 
public health, Dec. 22nd, 1888, No. 5849 (Sect. 3), 
having examined the clause 130 of the special rule for 
the hygienic vigilance, for food products, beverages 
and for articles of domestic use, approved with Royal 



FOREIGN SANITARY LAWS. 19 

decree Aug. 30th, 1890, No. 7045 (Sect. 3), having 
examined the list of the harmful colors compiled by the 
Minister of the Interior, according to Article 43 of 
the aforesaid law and communicated, with circular, 
July 8th, 1890, to all the Prefects of the kingdom, in 
order to avoid the danger of misinterpretations and to 
obtain that the determination of the Salts of Copper 
in the alimentary conserves, contemplated in the said 
list, takes place in all the kingdom with equal judg- 
ment as well as for the criminal effects ; having 
heard the opinion of the officers of the Board of 
Health and of the Ministers, upon the proposal of our 
Secretary of State for the Interior, we have decreed 
and decree: 

Art. 1. The preparations of Salts or Copper con- 
tained in the alimentary conserves (see Art. 130) 
must be calculated in metallic copper, and prohibited 
are only those conserves which contain more than one- 
tenth of a gram of metallic copper for each kilo of 
weight. 

Art. 2. — The list of the harmful colors which was 
modified by our Minister of the Interior, in the last line 
of the table- A in conformity with the former clause, is 
the following : 

List of harmful colors compiled by our Minister of 
the Interior in accordance with clause 43 of the law re- 
garding the public health. 

Harmful colors which must not be used in any way 
in the preparations of food products and beverage sub- 
stances in the coloration of paper for wrapping ali- 



20 



COAL TAR COLORS IN FOOD PRODUCTS. 



mentary substances and in the coloration of vessels 
which are employed to preserve the same, are : 

(A) Inorganic Colors. 



No. 



Color. 



1. Azure 



2. 
3. 

4. 



5. 



6, 



7. 
8. 
9. 

10. 
11. 
12. 

13. 



14. 
15. 



More common 
name. 



Indigo of Cop 
per. 



Harmful substance 
contained. 



Copper 



Azure Mountain Blue 
Azure Azure Ashes 
(Azurite) 
Chrome Yellow 



Yellow 



Yellow 



Cassels Yellow 



Yellow 



Naples Yellow 



Copper 
Copper 

Lead and Chrome 



Lead 



Yellow Orpiment 
Yellow Realgar 
Yellow Cadmium Sul 

phate 

Yellow Musive Aurum 
Yellow Lead Iodide 
Yellow Marsicot orLith- 



Yellow 

Yellow 
Green 



argyrum 
Yellow of Bar- 



ium 



Yellow Bottom 
of Gold 
Green Cinnabar 



Antimony and Lead 



Arsenic 
Arsenic 
Cadmium 

Tin 

Lead 

Lead 

Barium 



More noted synonyms 

or diversity of the 

same color. 



Mineral blue, Eng- 
lish blue, Ham- 
burg blue, lime 
blue, copper blue, 
Cassels blue, Neu- 
wied blue, Azur- 
ite, Armenian 
Stone, Azure Cris- 
ocolla. 



Chrome Yellow, 
Chrome Orange, 
Chrome Red, 
Cologne Yellow. 
Mineral Yellow, 
Montpelier Yel- 
low, 
Paris Yellow, 
Verona Yellow, 
Turner Yellow, 
Chemical Yellow. 
Antimoniate o f 
Lead, Naples 
Earth. 

Risigall. 
Brilliant Yellow. 



Zinc 
Lead 



Ultram. Yellow, 
Chromate of Bar- 
ium. 



Oil Green, 
Chrome Green, 
Naples Green. 



FOREIGN SANITARY LAWS. 



21 



(A) Inorganic Colors. — Continued. 



No. 


Color. 


More common 
name. 


Harmful Substance 
Contained. 


More noted synonyms 

or diversity of the 

same color. 


16. 


Green 


Green Millory 


Lead 




17. 


Green 


Bremen Green 


Copper 




18. 


Green 


Verdigris 


Copper 




19. 


Green 


Mountain Green 


Copper 


Malachite Green, 
Brunswick Green, 
Artificial M a 1 a - 
chite. 


20. 


Green 


Scheele Green 


Copper and Arsenic 


Original Green, 
Patented Green, 
Imperial Green, 
Cassels Green, 
Paris Green, 
Leipsig Green. 


20. 


Green 


Schweinfurt Green 


Copper and Arsenic 


Kirchberg Green. 


20. 


Green 


Vienna Green 


Copper and Arsenic 




20. 


Green 


Paolo Veronese 


Copper and Arsenic 




20. 


Green 


English Green 


Copper and Arsenic 




21. 


Green 


Mineral Green 


Arsenic, Lead, Cop- 
per, Mercury 




23. 


Red 


Cinnabar 


Mercury 




23. 


Red 


Red of Antimony 


Antimony 


Antimoniate o f 
Cinnabar. 


24. 


Red 


Minium 


Lead 


25. 


Red 


Chromateof Red 
Lead 


Lead 


Saturn Red. 


26. 


Red 


Lithargyrum 


Lead 




27. 


White 


White of Lead 


Lead 


White of Lead, 
Cerusa, 
Krems White, 
Kremitz White, 
Vienna White, 
London White, 
Holland White. 


28. 


White 


Sulphate of Lead 


Lead 




29. 


White 


White of Zinc 


Zinc 




30. 


White 


White of Grif- 
fiths 


Zinc 





Sulphate of copper is permitted to be used in con- 
serves of green vegetables at the proportion of a tenth 
of a gram, of metallic copper for each kilo of con- 
served material. 



22 COAL TAR COLORS IN FOOD PRODUCTS. 

(B.) Organic Colors. 

Forbidden to be used are : 

Gamboge — Artificial coloring matters from coal tar, 
except the following : 

Chrysoidin, Azoflavin, Eocellin, Ponceau, Bordeaux, 
Biebrich Scarlet, Naphthol Yellow S, Fuchsine, Gen- 
tian. 

Not allowed are the colors, either organic or inor- 
ganic, not stated in the present list, which contain 
harmful substances (mixtures of Antimony, Arsenic, 
Barium, Cadmium, Chrome, Mercury, Lead, Copper, 
Tin, Zinc) or other harmful substances. 

The present prohibition is not applicable in cases of 
coloration of vessels with incorporated harmful colors, 
when this coloration is made in such a way that it 
cannot be imparted to the beverages or to the food 
products they may come in contact with. 

We order, etc., Rome, February 7th, 1892, — Hum- 
bert. Nicotera. 

Royal Decree, January 29th, 1893, No. 132, regard- 
ing the adding of artificial coloring matters to the list 
of the harmful colors : 

Humbert I., by the Grace of God and the Will of 
the Nation, King of Italy, having examined the 
law regarding the public health and having examined 
the Royal Decree February Yth, 1892, No. 55, which 
approves the list of the harmful colors, and having 
heard the opinion of the meeting of the Board of 
Health, and having heard the meeting of the Minis- 
ters, on the proposal of our Minister and Secretary of 



FOREIGN SANITARY LAWS. 23 

State for the Interior affairs, we have decreed and 
decree : 

Art. 1 . Tropaeolin is to be added to all the artificial 
coloring matters from coal tar which are not included 
in the list of harmful colors, approved with Koyal 
Decree February 7th, 1892, No. 55, Part 1st, Table 
B., Organic Colors. The said table is then modified 
thus : 

(B.) Organic Colors. 

Forbidden are : 

Gamboge — Artificial coloring matters from coal tar, 
except the following : 

Chrysoidin, Tropaeolin, Azoflavin, Eocellin, Ponceau, 
Bordeaux, Biebrich Scarlet, Fuchsine, Naphthol Yel- 
low S, Gentian. 

We order, etc., Eome, January 29th, 1893. — Hum- 
bert. G. Giolitti. 

Eoyal Decree March 24th, 1895, No. 101, modify- 
ing the Part B. (Organic Colors) of the list of the 
harmful colors. 

Humbert I. , by the Grace of God and the Will of 
the Nation, King of Italy, having examined the law 
regarding the tutelage hygiene and public health ; 
having examined the Eoyal Decree February 7th, 
1892, No. 55, which approves the list of the harmful 
colors; having heard the opinion of the meeting of the 
Board of Health ; on the proposal of our Minister 
Secretary of State for the Interior affairs, President of 
the meeting of the Ministers, we have decreed and 
decree : 



24 COAL TAR COLORS IN FOOD PRODUCTS. 

Art. 1 The Part B. (Organic Colors) of the list of 
the harmful colors is modified as follows : 
Forbidden are : 

Gamboge. 
Picric Acid. 

Dinitrokresol — Mixture of the Alkaline salts of Din- 
itro-0-Kresol and Dinitro-p-Kresol (Substitute 
for Saffron — Victoria yellow, Victoria Orange, 
Aniline orange), Martins yellow — Dinitro-B- 
Naphthol (Naphthol yellow, Naphthalin yellow, 
Manchester yellow, Saffron yellow, Golden Yel- 
low, Methanilic yellow, Azo-Diphenilamin 
(Orange Color M. N. Tropseolin F.). 
The last but one line of the No. 1 is modified as 
follows. 

Not allowed are the colors, either organic or inor- 
ganic, not mentioned in the present list, which contain 
the same harmful substances (mixtures of antimony, 
arsenic, barium, cadmium, chrome, mercury, lead, 
copper, tin, zinc, under any form whatsoever) and all 
other harmful substances. 

We order, etc., Eome, March 24th, 1895. — Hum- 
bert. Signed F. Crispi. 

FKANCE. 

ARTIFICIAL COLORING AND FOOD STUFF HYGIENE. 

Ordinance of the Police Commissioner of June 15th, 
1862, concerning coloring of sweetmeats, food 
products, etc., and the utensils and the vessels of 
copper and other metals. 



FOREIGN SANITARY LAWS. 25 

Considering that grave accidents have occurred 
either by the use of poisonous materials for coloring 
purposes of sweetmeats, sugar plums, food products 
and liquors, either from the bad quality or adultera- 
tion of food stuffs or by the bad condition or the nature 
of the vessels in which the dealers in food stuffs, the 
restaurant keepers, the fruit dealers, the grocers, etc., 
prepare or conserve the food products which they 
offer for sale, and considering that accidents have 
been equally caused by papers colored with toxic col- 
ors in which sweetmeats and eatables are wrapped 
and were so offered to the public. (Law of August 

16-24, 1790, and of July 22d, 1791 ; the decree 

of the 3rd brumaire year IX. ; the law of March 

27th, 1851, and the articles 319, 320, 471, §15, and 477 

of the Penal Code ; the police ordinances of July 

20th, 1832, November 7th, 1838, September 22nd, 

1841, and February 28th, 1853 ; the ministerial 

instructions dating October 25th, 1851, concerning 
the waters of orange flowers, those of October 20th, 
1851, and April 7th, 1852, concerning the manufac- 
ture of syrups, and the one of April 20th, 1861, rela- 
tive to the tinning of utensils for the use of food 

products ; the reports of the Board of Public 

Hygiene and of Salubrity of the Department of the 
Seine, ordain as follows : 

Title I. 

Art.1. It is expressly forbidden to use any mineral 
stuff, excepting Prussian Blue, Ultramarine, chalk 
(carbonate of calcium) and ochres to color sweetmeats. 



26 COAL TAR COLORS IN FOOD PRODUCTS. 

sugar plums, pastilles, liquors and any sort of sweet- 
meats or other food products. 

It is equally forbidden to use for the coloring of 
sweetmeats, liquors, etc., vegetable stuffs injurious to 
health, especially the gamboge and aconite. The em- 
ployment of these materials is equally prohibited for 
the purpose of clarification of syrups and liquors. 

Art. 2. It is prohibited to wrap or to enclose 
sweetmeats in white papers smoothed or colored by 
mineral stuffs, except Prussian Blue, Ultramarine, 
ochres, and chalk. 

It is prohibited to place sweetmeats or conserved 
fruits in boxes papered inside or outside with papers 
colored with materials prohibited by the present ordi- 
nance and to cover them by cuts of these papers. 

The same law applies to flowers or other artificial 
objects serving for the decoration of sweetmeats, etc. 

Art. 3. It is prohibited to include any fulminat- 
ing preparation in the composition of sweetmeat 
envelopes. 

It is equally forbidden to use metallic wires for the 
support of flowers, fruits and other sugar and pastry 
confections. 

Art. 4. The wrapped envelopes must bear the 
name and address of the manufacturer or merchant ; 
the same applies to the bags in which the bonbons or 
sweetmeats will be offered to the public. 

The bottles containing colored liquors must bear the 
same indications. 

Art. 5. It is prohibited to introduce in the in- 
terior of bonbons and pastries metals or metallic com- 



FOREIGN SANITARY LAWS. 27 

positions of a nature forming compositions injurious 
to health. 

The metal leaves applied to sweetmeats must be of 
gold or fine silver only. 

The metal leaves introduced in the liquors must 
also be of gold or fine silver. 

Art. 6. The syrups containing glucose (Fecula 
syrup, starch syrup) must bear the common denomi- 
nations of ' ^ syrup de glucose " to avoid misunder- 
standing. Apart from this indication these bottles 
must bear the following label : * ' liqueur de f antaisie 
a Forgeat, a la groseille," etc., etc. 

Art. 7. Annually or oftener, if there is cause, 
visits must be made to the manufacturers and retail- 
ers in order to make sure that the conditions pre- 
scribed by the present ordinance are observed. 



Ordinance of the Police Commissioner of May 21, 
1885, concerning the manufacture, the sale and 
the offering for sale of colored liquors, sweet- 
meats, bonbons, sugar-plums and pastilles, the 
use of colored papers to wrap food stuffs and the 
offering for sale of food stuffs so wrapped. 

See : the law of August 16th-24th, 1790, and 

the one of July 22nd, 1791 ; the decrees of the 

Consuls of 12th messidor year VIII. and 3rd brumaire 

year IX. and the law of August 7th, 1850 ; the 

articles 319, 320, 471, §§15 and 477 of the Penal Code; 

the law of March 27th, 1^51; the Police 

ordinance of June 15th, 1862 ; the Police ordi- 
nance of June 8th, 1881 ; the Police ordinance of 

July 3rd, 1883 ; the law of April 5th, 1884; 



28 COAL TAR COLORS IN FOOD PRODUCTS. 

the ministerial instructions of March 30th, 1885 ; we 
ordain : 

Art. 1. Confectioners, distillers, grocers and all 
merchants in general are expressly forbidden to em- 
ploy for the coloring of sweetmeats, pastilles, sugar- 
plums, liquors and food products any of the below 
named materials : 

Mineral Colors : 

Copper compositions : Azurite, mountain blue. 

Lead compositions : Protoxide of lead, red lead, 
mine orange, lead oxychlorure, Cassels yellow. 
Turner yellow, Paris yellow, lead carbonate, 
white of lead, ceruse, white of silver, lead anti- 
moniate, lead chromate, Naples yellow, sulphate 
of lead, Chrome yellow, Cologne yellow. 

Chromate of barium. 

Arsenic compositions: Arsenate of copper, Scheele 
green, Schweinfurt green. 

Sulphate of Mercury : Vermilion. 

Organic Colors : 

Gamboge : Aconite. 

Colored stuffs deriving from aniline and its homo- 
logues, as the Fuchsine, Lyon blue, flavaniline, 
methylene blue. 

Phtaleines and their substituted derivatives. 

Eosin, erythrosin. 

Colored materials containing among their ele- 
ments the nitric vapor like the naphthol yellow, 
Victoria yellow. 

Colored materials prepared by the aid of diazoic 
compositions like tropseolines, xylidine red. 



FOREIGN SANITARY LAWS. 29 

Art. 2. The manufacturers and all merchants in 
general are forbidden to sell or to offer for sale sweet- 
meats, pastilles, sugar-plums, liquors and food stuffs 
colored by above mentioned colors. 

It is equally forbidden to employ for the wrapping 
of food stuffs papers colored with these colors and to 
offer for sale food stuffs thus wrapped. 

Art. 3. Attention is called to the ordinances of the 
Police of June 8th, 1881, and July 3rd, 1883. 

The Police ordinance of June ISth, 1862, is main- 
tained in those of its dispositions which are not con- 
trary to the present ordinance. 

Art. 4. The contraventions will be prosecuted ac- 
cording to the law before the competent courts. 



Ordinance of the Police Commissioner of December 
31st, 1890, concerning the coloration of food 
stuffs, the papers and envelopes used to wrap 
them and the vessels which will contain them. 

See : the laws of August 16-24, 1790, and July 

22nd, 1T91; the Consuls' decrees of 12th messi- 

dor year VIII. and 3rd brumaire year IX. and the 

law of August 7th, 1850 ; the Police ordinances 

of May 21st, 1885, and February 5th, 1889 ; the 

ministerial circulars of December 17th, 1888, and 
January 16th, 1889, relative to the employ of pewter 

leaves to wrap the food stuffs ; the advice 

emitted by the Consulting Committee of Public Hy- 
giene of France and the instructions of the Secretary 
of State of May 7th, 1889, August 29th and Septem- 
ber 29th, 1890 ; we ordain which follows : 

Art. 1. The use of the colors below mentioned is 



30 COAL TAB COLORS IN FOOD PRODUCTS. 

prohibited for the coloration of any food products of 
whatever description : 

Mineral Colors: 

Copper compositions : Azurite, mountain blue. 

Lead compositions : Protoxide of lead, red lead, 
mine orange, carbonate of lead, white of lead, 

ceruse, silver white ; lead oxychlorure (Cas- 

sels yellow, Turner yellow, Paris yellow) ; . . . . 

lead antimoniate (Naples yellow) ; sulphate 

of lead ; . . . . Chromate of lead (Chrome yellow, 
Cologne yellow). 

Chromate of Barium. 

Arsenic compositions : Arsenate of copper, Scheele 
green, Schweinfurt green. 

Sulphate of Mercury : Vermilion. 

Organic Coloi^s : 

Gamboge : Aconite. 

Coloring stuffs obtained from coal tar like fuch- 

sine, Lyons blue, flavaniline, methylene blue ; 

phtaleines and their substituted derivatives, 

eosin, erythrosin. 
Coloring stuffs prepared with the aid of diazoic 

compositions like tropaeolines, xydiline red. 

Art. 2. As an exception it is permitted to employ 
for the coloration of candies^ pastilles^ sweetmeats, 
ices, fruit pastries and certain liquors which are not 
naturally colored, like the green mint, the colors he- 
low meyitioned, deriving from coal tar, by reason of 



FOREIGN SANITARY LAWS. 31 

their restrained use and the small quantity of color- 
ing stuffs which these products contain : 
Pink Colors : 

Eosin (tetrabromo-fluorescein). 

Erythrosin (methylic and ethylic derivatives of 

eosin). 
Bengal Eose, Phloxin (iodine and bromine deriva- 
tives of fluorescein). 
Bordeaux Eed (obtained by the action of sulpho- 

naphthol derivatives upon diazoxylenes). 
Acid Fuchsine (without arsenic and prepared by 
the Coupier system). 
Yellow Colors : 

Acid Yellow, etc. (derivatives of sulpho naphthol). 
Blue Colors : 

Lyons Blue, Light Blue, Coupier Blue, etc. (de- 
rivatives of triphenilic rosaniline or dry diphe- 
nylamin). 
Green Colors : 
Mixtures of above blue and yellow colors. 
Malachite Green (chlorhydric ether of the tetra- 
metyldiamidotriphenylcarbinol). 
Violet Colors: 

Paris Violet ^or Violet of metylaniline. 
Art. 3. The use of colors below mentioned is pro- 
hibited for coloring of papers and cardboards employed 
to wrap food materials of any nature whatsoever. 

Mineral Colors : 
Copper compositions : Azurite, mountain blue. 
Lead compositions : Protoxyd of lead, red lead, 
mine orange ; . . . .carbonate of lead (white lead, 
ceruse, white silver) ; Lead oxychlorures 



32 COAL TAR COLORS IN FOOD PRODUCTS. 

(Cassels yellow, Turner yellow, Paris yellow) ; 

Lead antimoniate (Naples yellow) ; . . . . 

Lead sulphate ; . . . . Chromate of lead (Chrome 

yellow, Cologne yellow). 
Chromate of barium. 
Arsenic compositions : Arsenate of copper, Scheele 

green, Schweinfurt green. 

Organic Colors: 

Gamboge : Aconite. 

Art. 7. The offering for sale of products, objects 
and utensils, the manufacture of which is forbidden 
by the present ordinance, is prohibited the same as 
their manufacture. 

Art. 8. Attention is called to the Police ordinances 
of May 21st, 1885, and February 5th, 1889. 

Art. 9. Violations of this ordinance shall be pub- 
lished and posted and will be prosecuted in accordance 
with the law before the competent courts. 

Artificial Coloring. — Many liquors are not ac- 
cepted by the buyer unless they are colored. Certain 
colorations are given naturally by the infusions them- 
selves, like those of cassie, raspberries, etc. ; others by 
tinctures of amber, ben join of cachou, etc., in alcohol; 
finally many are taken from tinctorial materials like 
the cochineal by decoction in boiling water, etc. 

For coloring red is used cochineal prepared with 
alum and creme of tartar, cudbear (pulverized orchil), 
orchil paste, myrtle berries, hematine, coloring prin- 
ciple of campeche, sandal wood, red of lacque, wood 
of Fernambouc. 



FOREIGN SANITARY LAWS. 33 

The blue is obtained from indigo treated by sulphuric 
acid. The violet blue is obtained by the cochineal to 
which is added calcinated alum and a little liquid am- 
monia. The violet is also produced by the mixture of 
blue and red. The yellow is obtained from saffron, 
curcuma, ginger. The green is prepared by the yel- 
low, saffron for example, and indigo blue. The green 
color of plants, chlorophyll, is also extracted by boiling 
in alcohol leaves of balm mint, nettles, spinach, mint, 
wormwood, cassie, mountain wormwood. 

Finally yellow color is often obtained by the use of 
caramel, especially much used by the liquor dealers. 
The caramel is obtained by burning of sugar. 



The prejudice against the so-called aniline colors is 
easily explained. About the middle of the last century, 
when the first colors of this class appeared on the 
market, their toxic quality was quickly determined by 
proper experiments. These colors, especially Mauveine, 
Fuchsine, Aniline Blue, Aniline Red, etc., were at that 
time made from aniline and very frequently retained, 
as impurities, some parts of the arsenic and quicksilver 
which were employed in their manufacture. 

As was later proven, beyond a doubt, by proper 
physiological experiments, the poisonous quality of the 
colors was not due to the colors proper but to the above 
mentioned arsenic and quicksilver impurities. Sonnen- 
kalb, Bergeron, Clouet and others proved by experi- 
ments on human beings as well as on animals that 
even large doses of these colors could be partaken of 
without any detrimental effect whatsoever, * ^ if same 
were free of the poisonous impurities. ^^ But science 



34: COAL TAR COLORS IN FOOD PRODUCTS. 

did not stop at that, and to-day these colors are no 
longer produced with the aid of arsenic and quicksilver 
but by the Nitrobenzol process. 

Grandhomme used a so-produced fuchsine in his tests 
upon rabbits and chickens with the following results:* 

Two rabbits received for several weeks with their food 
daily each 0.5 gr. fuchsine. The animals remained per- 
fectly healthy and in good condition; the urine showed 
no albumen. Then the rabbits received for two weeks 
over 1 gr. daily without the slightest ill effects. The 
same result was obtained by continually feeding a 
chicken with oats which had been colored with fuchsine. 
Grandhomme also reports that at the Hoechster Farb- 
werke of 52 workingmen who were continually em- 
ployed in the Fuchsine room 

worked 3- 4 years, 
6 '' 4-6 '' 
11 '* 6-10 '' 
5 '' 11-18 '' 

none of these workingmen suffered of diarrhoea, colic, 
etc. Their urine was examined every Saturday, and 
after having worked all week in a room which natur- 
ally was always filled with the fine dust of Fuchsine, 
the urine was free of albumen. These and a great 
many similar tests made by absolutely reliable in- 
vestigators have proven beyond a doubt that these 
colors are harmless. Why then forbid their use? 
Simply because once upon a time they contained 
poisonous admixtures, or simply because once upon a 



* Weyl, Die Theerfarben. 



NITROSO COLORS. 35 

time there existed a well founded prejudice against 
these products. 

This should by no means indicate that all the coal 
tar colors are harmless. Just the contrary, there are 
certain colors the use of which should absolutely be for- 
bidden. By their thorough physiological experiments 
Weyl, Cazeneuve, Lepine, etc., have proven beyond 
a doubt the detrimental effect of certain coal tar colors 
and on account of their importance, I will copy their 
reports (translated and abbreviated). — Weyl, Die 
Theerfarhen. 

NiTROso Colors. 

I. — Dinitrosoresorcin. 
(CeH,N,0,) 

is produced by the action of sodium nitrite upon a 
solution of resorcin in diluted acetic acid under low 
temperature. 

Very little soluble in cold water or alcohol. More 
readily soluble in hot water and in hot alcohol. 

Insoluble in benzol or ether. It explodes if heated 
to 115°. 

The alkaline solutions discolor quickly into a 
brownish shade when exposed to air. 

The watery solution is colored green upon addition 
of ferrous salts. The green solution is discolored 
through reducing agents. 

It produces green color in cotton which had pre- 
viously been treated with iron salts. This color is fast 
to light and soap. 



36 COAL TAR COLORS IN FOOD PRODUCTS. 

The thereby produced green color is called resorcin 
green, Alsace green or solid green. 

Application through the Stomach. 
Test 2— Dog of 11550 Grams. 

June ISth — 2 gr. with a little soda by means of tube. 
'* 19th — Animal lively. Urine very little, dirty 
dark brown, neutral. Urine is colored dark green 
upon addition of iron salts. This green color is 
retained in diluted acetic or hydrochloric acid. 
2 gr. through tube. Urine 600 Ccm dark brown. 
Traces of albumen. Iron reaction very pronounced. 
A little alkaline. Does not reduce Fehling's 
solution. 

June 20th — 2 gr. through tube. Dog lively. Brown 
hard faeces. 

June 21st — 3 gr. through tube. Dog lively. No al- 
bumen. 

June 22nd — Dog lively. Weight 11140 gr. Loss about 
400 gr. 

Test 3— Dog of 5500 gr. 

July 13th — 1 gr. through tube. 
" 14th — Has eaten very little. Urine dark brown, 
almost black, colored green with ferrous sulphate, 
and forms gradually a green precipitate. 

July 15th — 2 gr. through tube. 
^' 16th — Urine colored green with ferrous oxide. 
No albumen. Does not reduce alkaline copper 
solution. Acids produce black flaky precipitate. 

July 17th — Dog lively. 3 gr. through tube. Urine 
alkaline. Color deep black. 

July 19th and 20th — Dog lively. Urine contains some 
albumen. Diluted sulphuric acid produces a flaky 



NITKOSO COLORS. 37 

brown precipitate. After filtration precipitate is 
readily dissolved in water and precipitated out of 
the filtered solution through diluted sulphuric 
acid. The body is colored green by ferrous oxide. 
The filtrate of the precipitate produced through 
the acid is not colored green again with ferrous 
oxide even after neutralizing. 

Hypodermic Application. 
Test 4— Dog of 5250 gr. 

July 4:th — 1 p. M. 1 gr. dissolved in 10 Ccm water and 
a little soda is injected under the skin of the back. 
In the evening very weak. Urine 50 Ccm, colored 
almost black. Addition of iron salts does not pro- 
duce green color. Presence of sulphates. Traces 
of albumen. Upon addition of acids a brown flaky 
precipitate is produced which is soluble in alkalies. 
Upon distillation with hydrochloric acid no preci- 
pitate could be obtained in the distillate with 
bromine water. 
July 5th — Dog indifferent. Eefuses absolutely all 

nourishment. Dead about 2 o'clock P. M. 
July 6th — Dissection. Corpse stiff and rigid. All 
abdominal organs hyperaemic, lungs hyperaemic, 
heart contains a great deal of non- coagulated blood. 
None of the examined parts of the corpse show 
green coloration with ferrous salts. 
The herewith cited tests show that the Dinitroso- 
resorcin is harmless to the dog even if administered in 
large doses through stomach, whereas upon hypoder- 
mic injection as little as 0.19 gr. per kilo of the animal 
is sufficien t to kill the dog within 24 hours. 



38 COAL TAR COLORS IN FOOD PRODUCTS. 

II. Naphthol Green B. 

(C^o Hi„ N^ Oi„ Fe Na, S,) 

Is the iron soda salt of the Nitrosonaphtholsulpho 
acid. 

It is a dark green powder, readily soluble in water, 
producing green color. If dusted in concentrated 
sulphuric acid appears golden yellow. No precipitate 
is produced upon diluting of the sulphuric acid with 
water. 

Diluted acids do not change the watery solution. 
Concentrated acids produce yellow color. Upon ad- 
dition of alkalies the green color is restored, providing 
it has not been affected for too long a period by the 
acid. 

The green solution is colored yellow when heated 
with a solution of caustic soda. Ether shaken with 
the alkaline solution remains colorless. The green 
solution gradually loses its color when heated with 
stannous chloride and hydrochloric acid. 

When heated upon a sheet of platinum a residue is 
obtained which contains sulj)hate of iron. 

Application Through the Stomach. 

Test 1. — Female Dog of 5800 grams. 

May 13th and 14th — Urine contains traces of albumen. 
^* 15th — One gr. dissolved in a little water through 

tube. 
May 16th — Animal very lively. Conjunctiva colored 

intensely green. Urine greenish. 1 gr. through 

tube. 



NITROSO COLORS. 39 

May 17th — 1 gr. stomach tube. Urine green. 
** 18th — 5 gr. (!) through tube. Animal lively. 

** 19th — Appetite undisturbed. Animal lively. 
Moderate diarrhoea. 

Test 2— Dog of 4800 gr. 

May 12th to 14th — Urine free of albumen. 
** 15th — 2 gr. through tube. Urine dirty yellow 
green. No albumen. No iron could be found by 
means of the well-known reagents. The urine 
cooked with fuming nitric acid for f of an hour 
barely contained traces of iron. 

May 16th — Dog normal. 
** 17th — 2 gr. through stomach tube. Animal un- 
changed. Lively. Eats good. Urine yellow 
green. No sugar. No albumen. 

May 18th — Very lively. Normal green colored faeces. 
Watery extract of the faeces when treated with 
ammonia or a solution of caustic soda discolors 
green. When treated with acids discolors red. 
Urine yellowish green. Urine acts the same as 
the watery extract of the faeces. No albumen. 
No sugar. The urine is gradually colored black, 
commencing at the top. By a mistake the ani- 
mal receives 2 gr. of safranin. Mild diarrhoea. 

Hypodermic Application. 

Test 3.— Female Dog of 5650 gr. 

May 20th to 23d— Urine free of albumen? 
** 24th — Hypodermic injection of 2 gr. in 25 water. 
Very lively. Has eaten. Conjunctiva, flesh sur- 
rounding teeth and gums colored green. 



ii 



40 COAL TAR COLORS IN FOOD PRODUCTS. 

May 25th — Hypodermic injection of 2 gr. in 25 water. 
Animal lively. 

May 26tli — 2 gr. hypodermic injection. 
27th — No injection. 
28th — 2 gr. hypodermic injection. 
^* 29th — No injection. Animal lively. No abscesses 
(see tests 4 and 5). Diarrhoea. 

Test 4.— Dog of 5015 gr. 

May 22d and 24th — Traces of albumen. 
^' 25th — Hypodermic injection of 2 gr. in 25 water. 
20 minutes after injection, conjunctiva, flesh 
around teeth and gums are colored green. Ani- 
mal lively. Little urine of an intensely green 
color. 

May 26th — 2 gr. hypodermic iDJection. Animal lively. 
27th — No injection. 

28th — 2 gr. hypodermic injection. Urine colored 
intensely green. Is colored intensely red with 
acids. 

May 29th — Animal very lean. No injection. Urine 
when made slightly acidulous with sulphuric acid 
dyes wool intensely dark green. 

May 30th-— Animal weak, feverish. Inner surface of 
ears green, as well as also the conjunctiva. 

June 1st — Many abscesses upon the back. 

^' 2d — Death. Six abscesses with pus upon the 
back. Dissection, exactly the same as in the fol- 
lowing test. 

Test 5.— Dog of 5600 gr. 

May 18th — Hypodermic injection 2 gr. in 25 water. 
20 minutes after injection the conjunctiva are 
colored green. 






NITROSO COLORS. 4:1 

May 19th — Hypodermic injection 2 gr. Urine green. 
20th — Hypodermic injection 2 gr. 
21st — 2 gr. Green urine dyes wool intensely 



(( 



green. 



n 



22d — Dog lively. No abscesses. Weight 5450 
gr., or a loss of about 150 gr. 
May 24th — Several abscesses upon the back. 
** 26th — Animal very weak. Was killed. Dissec- 
tion : Under the skin of the back thre^ big ab- 
scesses, one of which, when pressed, discharged a 
greenish pus without bad odor. Peritoneum, 
pericard, endocard, and pleura colored intensely 
green. Liver and spleen also colored green. The 
glomoeruli in the kidneys are not colored, whereas 
the urine channels are colored green. 

The tests 1 and 2 in which from one to five gr. 
daily of Naphthol Green have been applied directly to 
the stomach have proven the non-toxic quality of this 
color when partaken through the stomach, whereas 
hpyodermic applications in two or three cases pro- 
duced abscesses and septic fever. An infection 
through the syringe is not probable, as other animals 
upon whom the same instrument had been used re- 
mained absolutely free of abscesses. Also the cage 
could not be blamed. I rather must consider the 
color poisonous if applied hypodermically. 

The dog 3, I must surmise, was not treated suffi- 
ciently long and therefore appeared healthy when the 
test was finished. Very interesting is the pronounced 
green coloration of the conjunctiva and of the inner 
surface of the ear, appearing about J hour after in- 
jection. 



42 COAL TAR COLORS IN FOOD PRODUCTS. 

NITEO COLORS. 

I. Picric Acid. 

OH 
C,H3N30, = CeH2(0H)(N02)3 = NO^ /^ NO, 

NO3 

is Trinitrophenol. 

Is mostly produced through the effect of nitric acid 
upon phenolsulpho acid. Wlien dusted in sulphuric 
acid, colorless. 

The aqueous solution is not clouded upon addition 
of a few drops of diluted hydrochloric acid. 

Ether withdraws picric acid out of an acidulous 
solution. The ether becomes yellow colored. When 
cyanide of potassium is added the ether extract is 
colored reddish brown. The test with cyanide of 
potassium may also be made with a watery solution. 

A solution of copper oxide in ammonia produces a 
yellow crystalline precipitate even when greatly re- 
duced. The precipitate is dissolved to a clear liquid 
in hydrochloric acid. The solution in hot water is 
colored dark brownish red upon boiling with cyanide 
of potassium. 

Copper picrate is soluble in alcohol. 

Ammonium picrate does not produce a precipitate 
with a solution of caustic soda. 

Through a reduction with alcoholic sulphate of am- 
monium, Dinitroamidophenol is formed which is solu- 
ble with red color. 

The hydrochloric solution of stannous chloride re- 
duced to Triamidophenol, which is transformed into 
blue colored Diamidoamidophenol, upon addition of a 



NITRO COLORS. 43 

little ferric chloride. Ferric chloride produces with 
picric acid a reddish yellow precipitate, readily soluble 
in water. 

To observe picric acid in fiber or in food products, it 
must be isolated, and for this purpose it is best to ob- 
tain some in an ether solution; the latter is then shaken 
with some alkaline. With the alkaline of the picric 
acid the above mentioned tests can be made. 
/ Picric acid was formerly used a great deal 
alone and mixed with other colors to dye silk, wool 
(not cotton) and artificial flowers, yellow. 

It is supposed to have been used also as color for 
food and liquid products (beer). Even as a medicine 
(see below) it was prominent at one time. 

In Germany its use as a color for food products, etc., 
has been prohibited by law on account of its poison- 
ous qualities, since May 1st, lh88. The poisonous 
qualities of picric acid have been, however, frequently 
over-estimated. 

Erb gave a rabbit of a weight of ITOO gr. during 
90 days daily one grain (like 0.0(> gr.) potassium pic- 
ric. Occasionally it prcduced diarrhoea and loss of 
weight. Worse symptoms could not be observed. A 
rabbit of 2065 gr. died only after it had taken within 
19 days 42 grains (equal to 2.52 gr.) of the picric acid. 
A very young dog received from 
April 2lsfc to 26th, daily 4 gr. sodium picrate. 
From April 28th to May 9th — daily 6 grains sodium 
picrate, that is, in the course of about three 
weeks 96 grains (equal to 5.76 gr.) sodium picrate, 
without producing any dangerous symptoms. 
Then the same animal received on 



44: COAL TAR COLORS IN FOOD PRODUCTS. 

May 13th — 20 grains (like 1.2 gr.) sodium picrate at 
once. Within the following days the dog grew 
very weak. Considerable diarrhoea and Dyspnoea 
made their appearance. 

May 14th — Again 10 grains (0.6 gr.) were adminis- 
tered which, however, produced nausea. Even- 
ing again 6 grains (0.36 gr.). 

May 15th — The animal is lively and again receives 4 
grains (0.24 gr.) and on the same evening again 
12 grains (0.72 gr.). 

May 16th — Very weak. Hypodermic injection of 3 
grains (0.16 gr.) Sodium Picrate. Heavy vomit- 
ing follows. 

May ITth — Hypodermic injection of 12 grains (0.72 
gr.). 

May 18th and 19th — Animal improves remarkably. 
Besides a considerable yellow coloring of the con- 
junctiva and of the outer skin it shows no ab- 
normities. 

May 20th the poor animal dies after receiving 22 
grains (1.32 gr.) Potassium picrate. 

The dog had received the enormous dose of 175 grains 
(10.5 gr.) in a period of 4 weeks, of which 15 grains 
(0.9 gr.) Sodium resp. Potassium picrate had been ad- 
ministered hypodermically. After having partaken of 
143 grains (8.5 gr.) the dog was still fairly well. 

Dogs are, therefore, in spite of the prostration of 
strength produced by picric acid and in spite of the 
considerable destruction of the blood, very much able 
to resist this material. 

We are also very well informed of the effect of 



NITRO COLORS. 45 

picric acid and its salts upon the human body by 
means of therapeutic applications and through cases of 
poisoning. Daily doses of from 9 to 15 grains Potas- 
sium picrate (0.54 to 0.9 gr.) can be easily endured 
for quite some time by healthy and grown-up people. 
Generally after 24 hours appears a distinct yellow 
coloring of the skin and the conjunctiva. The urine 
becomes dark colored and contains besides other in- 
gredients, also small quantities of picric acid. 

Picric acid does not agree with children and weakly, 
feverish, grown-up people. 

Picric acid used to be considered formerly as a sub- 
stitute for quinine in intermittent fever. Doses of 5 
to 15 grains (0.3 to 0.9 gr.) potassium picrate per 
day were given apparently without results. 

It was also prescribed for the driving off of worms 
of the intestines. It is useless against Trichinosis 
and Cysticercus. For tape- worms, etc., however, the 
effect of the picrates has been praised. Picrate acid 
has furthermore been used successfully against whoop- 
ing-cough, dyspepsia, chlorosis, itch, chancre, etc. 

Only very few cases of poisoning of human beings 
by picric acid have been reported. None of these was 
fatal. 

In the case of Adler, a 16-year old girl took a tea- 
spoonful of picrate acid or about 3 to 5 gr. She 
vomited immediately and also had diarrhoea. The 
sclerotic and the skin of the entire body showed an 
intensive dark yellow, almost brown coloring, which 
made the patient look icteric. The visible mucous 
membranes were pale. The fingers of both extremi- 
ties were bent in the Metacarpo-Phalangeal joints, in 



46 COAL TAR COLORS IN FOOD PRODUCTS. 

the Phalangeal joints, however, stretched like in 
cramps, they could not be moved actively by the 
patient. The blood contained a great many white 
and few red blood particles. Ludwig could prove 
picric acid in the urine. After eight days, the girl 
had fully recovered. 

The aforesaid notices show conclusively, that while 
picric acid has to be counted among the poisonous 
materials, its toxic quality is considerably smaller than 
generally considered. However, to prohibit its use as 
coloring matter for food products and liquids, which 
has been done by imperial law, is fully justified. 

II. Saffronsurrogate (Dinitrokresol). 

As Saffronsurrogate, golden yellow, Victoria yellow, 
Victoria orange, aniline orange, a coloring matter has 
been named which principally represents Potassium 
or ammonium salts of Dinitrokresol. It is obtained 
by treating Kresolsulpho acids with nitric acid. 

Potassium and ammonium salts are readily soluble 
in alcohol or water. 

The concentrated solutions are orange colored ; the 
weaker are yellow colored. 

The salts of Saffronsurrogate explode upon heating. 
The commercial goods are mixed with about 40% 
hydrochlorate of ammonia so as to make them non- 
explosive and transportable. 

1. Dusted in concentrated sulphuric acid remains 
colorless. The sulphuric acid solution does not pro- 
duce a precipitate if diluted with water. 



NITRO COLORS. 47 

2. The aqueous solutions of Potassium or ammonium 
salts upon addition of muriatic acid become almost 
colorless or become a trifle yellowish colored. At the 
same time the free Dinitrokresol is precipitated in 
little yellow-colored needle shaped crystals. The pre- 
cipitate is soluble in alcohol. The free color acid in 
the acidulous solution is absorbed by ether and be- 
comes thereby faintly yellow colored. Alkali added 
to the ether extract is colored yellowish brown. 

3. The aqueous or alcoholic solution of the coloring 
matter becomes colored dark brown by heating with 
cyanide of potassium. 

4. The aqueous solutions of commercial Saffronsur- 
rogate are not precipitated even after long standing 
by ammoniacal copper solution. Sometimes after 
24 hours a little flaky precipitate is produced. 

5. The dry salts of the Dinitrokresol explode when 
heated. 

6. Ferric Chloride produces in the watery solution a 
slightly yellowish precipitate which is easily soluble in 
water. The solution heated with ferric chloride be- 
comes reddish colored. In cooling a flaky precipitate 
is produced. 

7. Liquor sodse does not produce any precipitate. 

8. Acid solution of stannous chloride produces : 

a. By addition of ammonia, red coloring. 

b. By addition of ferric chloride, orange yellow 

solution. 



48 COAL TAR COLORS IN FOOD PRODUCTS. 

Its use. — Almost exclusively for yellow coloring of 
food and liquid products, such as noodles, liquors and 
pastries. Orange color of silk and wool produced by 
Dinitrokresol fades easily and is therefore used but 
very rarely. 

Saffronsurrogate, as shown in the following ex- 
amples, is a strong poison. 

A. Tests on Eabbits. 
1 . Stomachical Application. 

Animals to whom 0.25 gr. Dinitrokresol salt dis- 
solved in a little water were administered by means 
of the stomach tube showed the following symptoms: 

Shortly after poisoning, the animals were usually 
as lively as before. They jumped about in the room 
and did not show the least abnormity. Soon, how- 
ever, the respiration became more frequent. The an- 
imal remained perfectly quiet in its place, and 
tumbled occasionally over on its side. In trying to 
walk ahead the hind legs were drawn after. 
The mouth touched the floor ; it was then raised 
again. The animal was still able to move ahead. 
The pupils were mostly dilated. In some cases, 
however, they become contracted shortly before 
death. Respiration after awhile became extraordi- 
narily frequent, it stopped occasionally, then the ani- 
mal was lying continually on its side, the head 
touched the floor, the eyes were opened wide, the con- 
junctiva bulbi (the white of the eyes) insensitive, the 
pupils greatly dilated, the extremities began to twitch, 
muscular cramps appeared. Cheyne-Stokes respira- 
tion phenomena were mostly observed. 



NITRO COLORS. 49 

The intervals between respirations became greater 
after a while, up to 10 to 15 seconds. Death set in 
through choking, frequently after the head was 
thrown backward and after ordinary short-lived 
cramps had preceded . In two cases (I and III) of the 
following table the entire proceeding occurred within 
between 20 to 30 minutes. The preparation used in 
these tests was, as already mentioned above, almost 
pure Dinitrokresolkalium. In test IX death only 
followed after two hours. The following reports of 
these tests will specify what has been said. 

Test IV. Eabbit of 680 gr. receives 0.17 gr. of 

the preparation. 
12:22 — Poisoning. 
12:30 — Animal jumps about lively. 
12:54 — Remains quiet. 

1:16 — Breathes through nostrils. 

1:52 — Head touches the floor. 

2 :00 — Long intermissions betw^een respirations. 

2:10 — Cheyne-Stokes. Intervals between breath- 
ing from 10 to 12 seconds. 

2:45— Death. 

Test IX. — Animal of 1797 gr. receives 0.45 gr. 
of the preparation. 
12 :00 — Poisoning. 
12:03 — Heavy Dyspnoea. 
12:10 — Animal lies on its side. 
3 2:12 — Stretch cramps. 
12:20 — Head thrown backwards. 
12:25— Dead. 



50 COAL TAR COLORS IN FOOD PRODUCTS. 

TABLE I. 

Test on Rabbit Application Through the Stomach. 





<D . 


Substances 








o 

525 


a to 


received 




03 




bo 




gr. 




tS 


Name of 




^j CO 




Dead After. 




the 


a 

j3 


fcCq 

•s.a 








Preparation. 


^ 


Abso- 


Per 




P5 




P5 


^§ 


lute. 


Kilo. 








I. 


890 


0.24 


0.27 


10 minutes. 




. 


II. 


670 


0.08 


0.12 


Remains alive. 




> Polyt. 


IIL 


640 


0.16 


0.25 


15 minutes. 




) 


IV. 
V. 


670 
1360 


0.17 
0.34 


0.25 
0.25 


21 

30 




>• Martius. 


VI. 
VIL 


1880 
750 


0.47 
0.187 


0.25 
0.25 


46 
25 




[ Schuster. 


VIII. 


680 


0.17* 


0,25 


143 




[ Sauppe. 


IX. 


1797 


45 


0.25 


20 




X. 


1610 


0.4 


0.24 


2 hours. 




^ Bremerhav. 


XI. 


1970 


0.5 


0.25 


2 hrs. 45 min. 




XII. 


1870 


0.45 


24 


2 " 15 " 




XIIL 
XIV. 


1750 
1690 


0.42 
0.42 


0.24 
0.25 


2 " 20 " 

3 " 30 " 




y Mittenzwey. 



* Some of the material was lost in the administration. 

2. Hypodermic Injection. 

I have tried hypodermic injections on a rabbit with 
a preparation from Bremerhaven only. The symptons 
were as above described, only the animal was killed 
quicker than by application through the stomach. 

Test XV.— Rabbit of 1825 gr. 

Received 0.2 gr. of the preparation from Bremer- 
haven. Hypodermic injection in luke-warm water 
(that is 0.11 gr. per kilo.). 

2 :04 — Injection. 

2;10 — Heavy Dyspnoea, beating of the flanks, ac- 



NITRO COLORS. 51 

tive expiration, very weak, extremities slide away 
from under the body of the animal. 

2 :4:0 — Head falls to one side, eyes wide open. 

3:00 — Animal lies continually on one side, very 
heavy breathing with long intervals. (Almost 
Cheyne- Stokes iype). Eeflection of the pupils disap- 
pears. 

3:15 — Animal dead. 

The second animal who, however, received only 
0.06 gr. per kilo injected hypodermically showed heavy 
Dyspnoea but survived. 

In the dissection of the animals to whom the poison 
was applied through the stomach, the stomach imme- 
diately attracted attention by its yellow color. The 
contents of the stomach were made acidulous with 
muriatic acid and washed out with ether. The ether 
extract colored green through chlorophyll (spectros- 
copic test), by shaking it with diluted solution of 
caustic soda transferred to the latter a substance 
which dissolved in alcohol with a yellowish red color. 
The green ether solution showed red fluorescence. 

The alkaline solution was freed from ether b}^ heat- 
ing. After making it acidulous with muriatic acid it 
produced a crystalline precipitate of the nature of 
Dinitrokresol. 

Most organs, especially liver and lungs contained 
much blood. 

B. Tests with Dogs. 

a. Stomachical Application. 

Animals to whom saffronsurrogate is applied to the 
stomach through a tube show very characteristic 



52 COAL TAR COLORS IN FOOD PRODUCTS. 

symptoms. In every case single or repeated vomiting 
is produced. Diarrhoea is also frequently observed. 
If the dog has thus discharged the biggest part of the 
poison, it acts again within ten or fifteen minutes 
like a normal animal, it walks about, answers a call 
and eats the food offered. 

Generally, however, the animal retains enough 
Dinitrokresol so that the other symptoms of the poison- 
ing can be observed. In this case, a peculiar trem- 
bling of the whole body follows about ten to twenty 
minutes after the vomiting. Convulsive, frequently 
unsuccessful attempts to vomit follow, but generally 
only produce tough yellow-colored phlegm. Breath- 
ing is produced with difficulty and accompanied by 
active expirations. The animal is not able to keep 
on its legs. Saliva appears. It lies on one side. 
Cramps of the extremities set in which appear like an 
attack in which the animal tries to paw the air. 
Death generally follows with the 3rd or 4th attack. 

Following are a few reports of the tests : 

Test I.— Dog of 6230 gr. 

Eeceives on January 8, 1888, about 1.5 gr. Dinitro- 
kresol of the collection of the laboratory in 50 to 60 
luke-warm water by means of tube. 

12:20— Injection. 

12:30 — Kepeated vomiting. 

12:40 — Trembles considerably. Hardly able to re- 
main on its legs. Repeated vomiting. 

12:45 — Repeated convulsive efforts to vomit. Ani- 
mal lies down on its side. 

12:49 — Cramps. Animal lies on its side. 



NITRO COLORS. 53 

12:52 — Diarrhoea. Salivation. 

1 :0u — Animal sleeps. 

2:00 — Animal absoluty recovered and well. 

Test III— Dog of 5500 gr. 

Receives on January 21st, 1888, 0.30 gr. Dinitro- 
kresol of the laboratoy collection by means of tube. 

12:10 — Injection. 

12:1 5 — Vomiting. 

12:20— Diarrhoea. 

12 :25 — Animal falls on its side. Cramps. Repeated 
vomiting. Yellow tenacious white phlegm is dis- 
charged. 

12:27 — Repeated severer attacks of convulsions. 
Animal lies on its side. Mouth wide open, tetanic. 

12:35— Third attack. 

12:45— Fourth attack. 

12:50 — Animal dead. Muscles stiff. Dissection: 
Very little contents in the stomach. A few crystals 
of Dinitrokresol. Liver, intestines, lungs hypersemic. 
No Methaemoglobin in the blood. 

Test V. — Newfoundland Bastard of 14.5 kilos. 

Receives on January 26th, 0.7 gr. Dinitrokresol, 
preparation of the Polytechnic Institute, in a little 
milk through the stomach tube. 

1 :55 — Injection. 

2:20 — Animal quiet. 

2:35 — Dyspnoea. Whimpers aloud. 

2 :40 — Salivation. 

2 :45 — Passes urine which contains Dinitrokresol salt. 

2 :46 — Vomiting. 

2:50 — Very restless. 



54 COAL TAR COLORS IN FOOD PRODUCTS. 

3:30 — Cramps. Whimpers aloud. 

3 :03 — Vomiting. 

3;15 — Considerable Dyspnoea. Lies on its side. 
Strong attack of convulsions. Does not respond to 
strong irritations. 

3:25 — Dog livelier. 

3:31 — Little Dyspnoea. 

4:00 — Lively and completely recovered. 

See Table II for complete list of the various tests. 

h. Hypodermic Injection. 
Through hypodermic injections I hoped to avoid the 
vomiting produced by stomachical applications. The 
tests proved this calculation to be wrong. 

Test VI.— Dog of 6230 gr. 

Eeceives on January 24th, 1888, 0.1 gr. Dinitro- 
kresol, preparation of the laboratory collection, in 
about 10 cc. water by hypodermic injection. The 
animal had received before 0.3 gr. directly into the 
stomach ; however, in spite of clearly shown symptoms 
of poisoning it survived. 

1:21 — Injection. 

1:30 — Heavy Dyspnoea. Vomiting. 

1 :30 — Trembling. Light attack of convulsions. 

1:57 — Salivation. Light attack of convulsions. 

2;00 — Cramps. Tetanus of the Masseter. Tena- 
cious phlegm in front of its mouth. 

2:05 — Heavy Dyspnoea. Animal lies on its side. 

2:10 — Erepeated attacks of convulsions and cramps. 
Dog does not respond any more to calls, not even to 
strong irritations. 



NITRO COLORS. 55 

2:15 — Dead. Muscles stiff. Dissection: As above. 
No Methaemoglobin in the blood. 

Test VII.— Dog of 14.5 kilos. 

Receives January 26th, the following doses of the 
preparation of the laboratory collection by hypodermic 
injection. 

(Three days before the animal had received a heavy 
dose (O.T gr.) of the poison, stomachical application. 
In spite of distinct symptoms of poisoning the dog re- 
mained alive. 

10:40 — 0.1 hypodermic injection. 

Until 12:15 — A little weak, then livelier. 

12:20 — 0.1 hypodermic injection. Animal weak. 

2:00 — 0.2 hypodermic injection. 

2:30 — Active expiration. Abdominal breathing. 

2:45 — Dyspnoea. Reponds to a call by wagging of 
the tail. Weak attack of convulsions. Later com- 
pletely normal. 

Test VIII.— Dog of 3420 gr. 

Receives January 27th, 1888, 0.1 gr. of the prepara- 
tion of Bremerhaven, in about 10 ccm. water by hypo- 
dermic injection. 

10:30 — Injection of 0.1 gr. 

11:06— Vomiting. 

11:27 — Renewed vomiting. 

12:00— Same. 

12:50 — Hypodermic injection, 0.2. 

12:55 — Vomiting of yellowish material. 

1:10 — Convulsive attempts to vomit. Vomiting of 
yellowish material. 

1:11 — Weak attack of cramps. 



56 COAL TAR C0L0R8 IN FOOD PRODUCTS. 

1:16 — Animal lies on its side. Strong attack of 
cramps. Cramps. Tetanus of the Masseter. Mouth 
wide open. 

1:18 — Very strong dyspnoea. Continued cramps. 

1 :20 — Dead. Muscles stiff. Result of dissection as 
usual. 

Test IX.— Dog of 5690 gr. 

Receives 0.1 Saffronsurrogate from Mittenzwey 
(0.017 per kilo.) in about 25 ccm. lukewarm water, 
hypodermic injection. 

10:40 — Injection 0.1. 

10:48 — Hard faeces. Licks the spot where injection 
has been made. 

10:51 — Breathes very fast. 

11:35— Sits down. 

11:50 — Apparently normal. 

12:15 — 0.2 injection (hypodermic). 

12:25 — Breathing faster. 

12:26— Vomits. 

12:27— '' 

12:30— '' Trembles. 

12:31 — Vomits yellow tenacious phlegm. 

12:32 — Weak attack of convulsions. Animal lies 
on its side. 

12:33 — Tries to get up. 

12:35 — Heavy attack. Cramp. Cramp of the Mas- 
seter. White foam in front of its mouth. 

12:36 — Heavy attack of convulsions. 

12:37 — Still in convulsions. Pupil reacts. 

12:40 — By irritation no attack is produced. Very 
fast breathing. Animal lies on its side. 



NITRO COLORS. 



57 



12:45 — Third attack of convulsions and cramps. 
12:49~Fourth 
12:52— Fifth 
12:55— Sixth 

1:00 — Seventh 

1 :02 — Eighth 

1 :05— Ninth 

1:08— Tenth 

1:15— Eleventh 

1 :26— Respiration 108 ( 



120( 
148 ( 
180 ( 
'' 120 ( 

Breathes slower. 



a 



a 



Lies on its side. Opens 



1:32— 

1:38— 

1:39— 

1:45— 

1:50- 
its eyes. 

1:52 — Makes spontaneous movements with its tail. 

2:00 — Breathes a great deal more quietly. 

2:10 — Respiration 90. 

2:25 — Moves the head spontaneously. 

2:30— Wags its tail a little. 

2:45 — Has recuperated. Still lies on its side. 
Lives on the following day and is apparently com- 
pletely normal. 



58 



COAL TAR COLORS IN FOOD PRODUCTS. 



TABLE II. 

Tests on Dogs. 





^ 




d 


o 


1.1 


^ 


-^ 


&0 


■^ d 


p 


Cj_| "-> 




O 33 


a 


-^ 'eS 


a 


fna 


«■ 


9i 




^ 


I. 


6230 


II. 


5500 


III. 


5500 


IV. 


6230 


V. 


14500 


VI. 


6230 


VII. 


14500 


VIII. 


•3420 


IX. 


5690 



Substances 

received 

gr. 



Abso- 
lute. 



Per 
Kilo. 



Dead After. 



a. Stomachical Application. 



1.5 


0.2 


0.3 


0.055 


0.3 


0.055 


0.3 


0.048 


0.7 


0.05 



40 minutes. 



b. Hypodermic Injection. 



0.1 


0.016 


a) 0.1 


0.007 


b)0.1 


0.007 


c)0.2 


0.014 


0.1 


0.029 


a) 0.1 


0.017 


b)0.2 


0.035 



75 minutes. 



170 minutes. 



S-i 

a 

o 



Recup- 
erates. 



Recup- 
erates. 



Recup- 
erates. 



) Recup 
C erates. 



Name of the 
Preparation. 



j- Polytech- 
nic, 



I Polytech- 



nic. 



Bremerhaven 
I Mitten- 
\ zwey. 



The above table requires little explanation. It 
could appear astonishing that animals which received 
0.05 gr. Dinitrokresol salt through the stomach 
(Tests II-V) did not die in all cases. This, however, 
is easily understood if one considers that every appli- 
cation of a dose is a deception which produces 
as the one in question immediate vomiting. It de- 
pends clearly on chances which the experimenter 



NITRO COLORS. 59 

does not control, whether much, little, or as good as 
nothing of the administered saffronsurrogate become 
effective. The same is especially the case with Test I. 

By hypodermic injection the proportions are as fol- 
lows : Tests VI and VII are to be compared because 
they are undertaken with the same preparations. The 
animal which received 7 mgr. per kilo. (Tests Vila and 
Vllb) remained alive. 16 mgr. per kilo, killed in Test 
VI. 14 mgr. per kilo, were not fatal for the big 
dog of 14.5 kilo, in Test VIIc. 29 mgr. per kilo, 
killed in Test VIII almost double the quantity of 
the dose which produced death in Test VI. But the 
Bremerhaven preparation used in Test VIII con- 
tained, as is mentioned later more explicitly, about 
S3fo ammonium chloride, while the preparations of the 
collection of the laboratory used in all the other tests 
were almost pure Dinitrokresolkalium. 

The animal of Test IX (test was made with the 
preparation of Mittenzwey) was near death, as the 
test report indicates. 

The tests made on the dog showed the following 
characteristic symptoms of poisoning : * 

It is immaterial whether the poison was applied to 
the stomach or hypodermically, in all cases nausea and 
vomiting were the first signs of poisoning. Active 
expiration and dyspnoea accompanied. Then followed 
salivation and characteristic trembling of the whole 
body. 

The animal mostly lay helpless on its side. 

The first attacks of convulsions appeared, and 
mostly in the form of severe cramps. A second and 
third attack of convulsions followed. 



60 COAL TAR COLORS IN FOOD PRODUCTS. 

The animals usually died during such an attack. 
A few minutes after death the muscles were found to 
be stiff and rigid (rigor mortis). 

In several cases the animals recuperated entirely 
after one to two hours. 

As dosis toxica resulted for the dog by hypodermic 
injection T to 10 mgr. per kilo, against the dosis 
lethalis 16 mgr. per kilo, for an almost pure Dinitro- 
kresolkalium, 29 mgr. per kilo, for the commercial 
preparation with over S0% ammonium chloride. 

As appears from the following formulas, saffron- 
surrogate resembles carbolic acid and picric acid : 



CeHjOH 


p XT ^H 


Carbolic Acid 


Methylcarbolic Acid 


Phenol 


Kresol 


OH 


OH 


/ 


/ 


CeH^-(N02)3 


^6^2 = ^^Z 




// 


Picric Acid 


(NO,), 


Trinitrophenol 


Saffronsurrogate 




Dinitrokresol 



The poisoning symptoms of the Dinitrokresol cor- 
respond also in the main points with those of carbolic 
acid as are shown on the rabbit by E. Salkowski, 
on the dog by J. Munk. 

One could almost call a poisoning by saffronsurro- 
gate a carbolic acid poisoning. Only Dinitrokresol 
is considerably more poisonous than the carbolic 
acid, as the following summary will show: 



NITRO COLORS. 



61 





Application. 


Dosis Lethalis Gr. 
per Kilo. 

Rabbit. Dog. 


Cart 
DinitrokresoL. 
Dinitrokresol. . 


)olic Acid. 

Commercial Goods. . 
Pure 


Stomach 

Hypodermic 
Injection.. 


0.45 
I 0.25 


0.5 

0.039 
0.016 









In this table the per os applied doses are compared 
with those which were given hypodermically. This 
was done because the Saffronsurrogate if applied to the 
stomach causes vomiting, and it is, therefore, difficult 
to establish exact doses, furthermore because it seems 
that the dosis lethalis of carbolic acid by hypodermic 
injection for the dog has not been established. Tak- 
ing it for granted, however, that carbolic acid affects 
about 60% stronger by hypodermic injection, which is 
surely exaggerated, then the poisonous quality of the 
Dinitrokresol is still considerably superior to Phenol. 

A characteristic difference between Dinitrokresol 
and carbolic acid poisoning is shown by the producing 
of vomiting of the first substance. 

The aforesaid communicated tests prove the Dini- 
trokresol to be a poison. It is, therefore, fully justified 
that the State should prohibit the free handling of 
such a dangerous stuff, and also prohibit its use for 
coloring or food products, liquids and also of fabrics. 

A still better cause for the above is shown in the 
case of fatal poisoning by Saffronsurrogate (Dini- 
trokresol) of the human being, for the first knowledge 



62 COAL TAR COLORS IN FOOD PRODUCTS. 

of which I am indebted to the courtesy of Dr. With, 
Police Surgeon in Bremerhaven. The circumstances 
are in short as follows: 

On August 9, 1887, J., a married woman in Brem- 
erhaven, whose menstruation did not set in, sent for 
15 Pfg. Saffron. She swallowed the red powder 8 
o'clock in the morning, was taken ill with vomiting, 
and died on the same day about 1 o'clock noon. 

Dissection undertaken on the following day. The 
skins of the abdomen were pale yellow, also the con- 
junctiva and the mucous membrane of the mouth. 
No acid impressions ia the mouth. In the pericar- 
dium dark yellow serum. No liquids in the pleura. 
In the bronchial tubes yellowish green liquid substance, 
also in the lungs. In the small intestine no abnormal 
contents. The mucous membranes of the stomach were 
colored with a brownish yellow pulp. The contents 
of the stomach showed upon diluting with water in a 
thin layer an intensely yellow, in a thick layer a 
brownish yellow red color. The urine has the same 
peculiar yellow coloring as the skins of the abdomen 
of the corpse. The urine contained no gall coloring. 
I cannot say anything about the uterus. 

The County Court in Bremerhaven sent to me about 
10 gr. of the powder of which the dead woman par- 
took. 

I have used same for toxicological and chemical 
tests. 

a. Toxicological Tests. 

They have already been described at length before. 
For comparison I shall again show the tests made by 



NITRO COLORS. 



63 



me with the Bremerhaven preparation, and add to same 
the experiments made with the commercial product 
of Mittenzwey, for the reason, as will be shown later, 
that both products were identical. 

Tests on Animals with the Preparations from 
Bremerhaven and Mittenztvey. 



o. 



Name of the 
Preparation. 



Bremerhaven. 
<( 

Mittenzwey. . 

Bremerhaven. 
Mittenzwey. . 



Animal . 



Rabbit 



Dog 



How 
Applied. 



Stomach. . . 



Hypodermic 
Stomach. . . . 

Hypodermic 





Substances 




Received. 


Weight 
of tiie 






bo 


bO 


Animals 


a> 




gr. 


•^-i 
3 


O^ 




o 


M 










< 


Pk 


1610 


0.4 


0.24 


1970 


0.5 


0.25 


1870 


0.45 


0.24 


1825 


0.2 


0.109 


1750 


0.42 


0.24 


1690 


0.42 


0.25 


3420 


0.1 


0.029 


5690 


a)U.l 


0.017 




b)0.2 


0.035 



Remarks. 



Dead after 2 days. 

Dead after 2hrs. 45m. 
" 2 " 15 " 
" 1 '' 11 " 
" 2 " 20 " 
" 2 " 30 '* 
" 2 " 80 '♦ 



>■ Recuperates. 



These tests show that the Bremerhaven preparation 
is a material which is capable of killing rabbits and 
dogs by stomachical application as well as by hypo- 
dermic injection, even in small doses, after a short 
time. 

The characteristic symptoms under which the ani- 
mals died have been described above. 



h. Chemical Test. 
The Bremerhaven preparation consisted of 
orange red, soft, indistinctly crystalline powder. 



an 



64 COAL TAR COLORS IN FOOD PRODUCTS. 

When heated in a tube closed on one side it decom- 
poses discharging at the same time nitrous fumes ; 
when heated upon platinum it decomposes under 
sizzling. 

In dissolving with water of ordinary temperature, 
one part of the powder dissolved with orange color, 
another part remained as a brownish black substance 
resembling tar ; the latter when treated with warm 
water was completely dissolved . 

The solution of the powder in water dyed silk 
and wool orange. 

The color could be drawn off completely by hot 
water. The watery solution was not precipitated by 
liquor sodsB. Ammoniacal copper solution produced a 
very small flaky precipitate after 24 hours only. 
Upon addition of diluted sulphuric acid or muriatic 
acid to the watery solution a crystalline precipitate 
was produced. The same was repeatedly re-crystal- 
lized out of hot water ; the yellow needle shaped 
crystals melted at 79 to 80 degrees. (The Dinitro-p- 
kresol melts at 84 degrees, the Dinitro-o-kresol at 86 
degrees.) The crystals contained nitrogen and ex- 
ploded when heated quickly and were soluble in alcohol 
and in alkalies with orange color. 

Unquestionably we had a mixture of Dinitro-Para- 
and Dinitro-Ortho-Kresol. There was not enough 
material for a further separation and for burning 
purposes. A quantitative definition of the substances 
contained in the Bremerhaven preparation was tried 
after the following two methods. 

A. 2 gr. of the red powder were dissolved in about 
300 ccm. of hot water which was mixed when still 



NITRO COLORS. 65 

warm with diluted sulphuric acid and set aside for 48 
hours. After that time the precipitate was col- 
lected on weighed filter, washed a little with water, 
dried in vacuum and weighed. The yellow filtrate 
was shaken with ether until discolored. The ether 
extract was evaporated in a dish which had been 
weighed. The residue was weighed after drying in 
vacuum over sulphuric acid and considered the same 
as the matter collected on the filter, as Dim'tro- 
kresol. 

The watery, almost colorless filtrate, freed from 
ether, was increased to J liter; same contained Potas- 
sium, Ammoniac and Chlorine. The chlorine was 
etermined by titrating with a silver solution and 
considered as ammonium chloride (NH4 CI), while the 
Potassium on account of the weighed Dinitrokresol 
was taken into account as Dinitrokresol potassium. 

In this way I received out of 2 gr. substance : 

Dinitrokresol by filling 0.7065 

'' out of the ether extract. 0.330 



Total Dinitrokresol 1.0365 

= 51. S% Dinitrokresol. 

Furthermore :— 0.4524 CI = 0.67 NH4 CI— 33.5% 
NH4 CI. 

B. In the second experiment 2 gr. of powder were 
dissolved in about 300 gr. water to which was added 
an excess of diluted sulphuric acid, then immediately 
shaken with ether until discolored. The residue of 
the ether extract was dried in vacuum over sulphuric 
acid and then weighed. 



66 COAL TAR COLORS IN FOOD PR0DX3CTS. 

Obtained : 

Dinitrokresol 0.984 gr. == 49.2%. 

The preparation in average therefore contained in 
two tests — '- — — ^=50,5^ Dinitrokresol, which 

is equal to 60% Dinitrokresolkalium. 

Add 33.5^ of Ammoniiimchloride. The rest has to 
be taken in account as moisture and as loss. 

60 fo Dinitrokresolkalium. 
ZS.5% ammonium chloride. 
6.5% moisture and loss. 



100.0^ 



When I compared the Bremerhaven powder with 
the commercial Saffronsurrogates which were con- 
tained in my collection, it was found that the Saffron- 
surrogate of Mittenzwey in Poelbitz first in its color 
and then also in its chemical composition was identi- 
cal with the Bremerhaven powders. 

This chemical identity is further proven by a com- 
plete identity of the toxicological effects of both prep- 
arations. This point has already been described 
more explicitly above. 

The court proceedings have furthermore proven 
that said Bremerhaven preparation was obtained from 
Mittenzwey. 

It can be proven with safety on account of the toxi- 
cological and chemical tests which I stated, that said 
woman in Bremerhaven died through poisoning with 
Saffronsurrogate. 



NITRO COLORS. 6T 

With the intention to produce abortion through a 
saffron powder she took in place ' of the genuine saf- 
fron (Crocus) the Saff ronsurrogate given to her. The 
deathly powder cost 15 Pfg. As a kilo, of Saff ronsur- 
rogate is sold by the manufacturer for about 23 
marks and as the retail dealer makes at least a profit 
of 50%, the woman must have received for 15 Pfg. 
about 4.5 gr. of the poison. Had the woman weighed 
75 kilo, then the fatal dose of the Saffronsurrogate of 
Mittenzwey would have to be considered as 0.06 gr. 
per kilo, human being. It has also to be emphasized 
that the Bremerhaven preparation could not have 
contained considerable quantities of other nitro com- 
binations, especially of picric acid. I have convinced 
myself that the usual and commercial nitro coloring 
materials are precipitated by considerable dilution with 
ammoniacal copper solution with the exception of 
Dinitrokresol. Brilliant Yellow which also forms a 
comparatively easily soluble copper salt can not have 
been an adulterant of the preparation as this is pre- 
cipitated through solution of caustic soda and ought 
to have yielded a characteristic re -action with ferric 
chloride. 

The Bremerhaven case proves that Dinitrokresol 
even in small doses is a fatal poison for the human 
being. The free handling of such a substance ought 
to be prohibited by law. 

3. Martius Yellow. 
Co H5 N, O5 Na. 
Martius yellow is named after its discoverer, Dr. C. 
A. Martius, in Berlin. It is also designated as naph- 



68 COAL TAR COLORS IN FOOD PRODUCTS. 

thol yellow, naphthaline yellow, Manchester yellow, 
Saffron yellow, Jaune d'or. 

1. Dusted in concentrated sulphuric acid, reddish 
yellow. The solution of color in sulphuric acid be- 
comes milky and cloudy when diluted with water. If 
ether is added to the sulphuric acid solution diluted 
with water, the ether becomes only a little yellowish 
colored. If the ether is poured off very carefully, it 
becomes deep yellow colored upon addition of liquor 
sodse. Even the alkaline solution becomes yellow to 
brownish yellow colored. 

2. With cyanide of potassium the watery color so- 
lution, after considerable boiling, shows first a 
brown color; then the entire liquid colors itself in- 
tensely dark brown. The reaction with cyanide of 
potassium is the same, as it seems, in all nitro colors. 

3. Upon heating it explodes. 

4. The watery solution becomes cloudy upon addi- 
tion of a little acid. 

5. The watery solution is precipitated in flakes after 
a little while through liquor sodae. The precipitate is 
reddish. 

Picric acid, Dinitrokresol, Naphthol Yellow S and 
Aurantia are not precipitated by a solution of caustic 
soda. 

6. Ammoniacal copper solution produces a crystal- 
line precipitate, even when greatly diluted. The cop- 
per salt is soluble in hot water and produces with con- 
centrated sulphuric acid a precipitate of free Dinitro- 
naphthol with which the ether test described under 
No. 1 can be made. 



NITRO COLORS. 69 

7. Through reduction with a muriatic acid solution 
of stannous chloride is produced: 

a. By addition of ammonia, an orange-red solution. 

b. By addition of ferric chloride, an almost fuchsine 
red liquid. 

8. Ferric chloride produces a yellowish precipitate 
which is colored red like the solution upon boiling. 

Its uses: As Martins yellow discolors considerably 
and evaporates partly upon heating, it is used but 
very little for dyeing of wool and silk. 

After G. Schulz it is used for wool and carpet 
printing. 

It is used for coloring of food products (macaroni) 
in France and Italy. 

There are some good tests of Cazeneuve & Lepine 
regarding the effects of Martins yellow upon animal 
organisms. 

Cazeneuve and Lepine experimented with the sodium 
salt of Martins yellow. 

To a dog of 7 kilos were given daily 0.05 gr. (per 
kilo?) of the pulverized color through the throat. 
Beginning with the second day, diarrhoea and vomit- 
ing of yellow colored material. The animal refused 
to take any nourishment except milk. Since the 4th 
test day dyspnoea and 41 degrees in recto. These 
symptoms increase. On the 6th day, gasping respira- 
tion. Rectum temperature 42 degrees C. Desire to 
eat has disappeared. The urine contains the applied 
coloring matter and albumen. The animal dies on 
the sixth day. 

Dissection — Several intestines yellow colored. 

Second test animal; dog of 22 kilos; received 0.4 



70 COAL TAR COLORS IN FOOD PRODUCTS. 

gr. (per kilo?) suspended in syrup. The following 
day 0.5 gr. Poisoning symptoms same as dog No. 1. 
It is killed. 

Dissection — No coloring of the intestines. Ex- 
tended Hypersemia of same. 

Further experiments were made in such manner 
that the experimenters injected into the vena femo- 
ralis of dogs of 10 to 25 kilos 0.03 to 0.06 gr. of the 
coloring matter dissolved in a 0.7 per cent, salt solu- 
tion (per kilo animal). The temperature of the dogs 
rose to 44 degrees. Heavy dyspnoea set it. Death 
occurred f to 1^ hours after injection. After dose of 
0.1 per kilo injected in the blood, poisoning symptoms 
as already described appeared also. The animals re- 
cuperated however. 

I then gave to two rabbits of 1797 gr. and of 2100 
gr. each 0.55 gr. of the ammonium salt and one gr. of 
the potassium salt of Martins yellow. No poisoning 
symptoms appeared in these animals. 

The following experiments were made with dogs. 
The more readily soluble sodium salt of Martius yel- 
low was used. It forms yellow-red needles and was 
made from calcium salt. 

Experiment I. 
Dog of 6850 gr. 

March 10, 1888 — 1 o'clock — 0.5 gr. Martius yellow 
(Na. salt) in about 25 water applied through 
stomach tube. 
1:10 — Considerable nausea. 
About 6 o'clock — Vomiting. 



NITRO COLORS. 7l 

March 11- — 10 o'clock A. m. — Animal very weak. Tem- 
perature in recto 40.8 degrees. Vomiting. Diar- 
rhoea. In the urine traces of albumen. The urine 
a little darker colored than the salts applied. The 
urine made strongly acidulous with sulphuric 
acid produces a weakly yellow-colored ether ex- 
tract. If sodium is added, the ether is colored a 
more saturated yellow, the same also the alkaline 
solution. 

Upon addition of acids (H CI or H^ SO 4) the 
urine becomes cloudy through separated (free) 
Dinitronaphthol. No injections made. 

March 12 — 1:00 — 0.5 through stomach tube. 

1:10 — Vomiting. Then hvely. Normal respira- 
tion. 

March 13 — Diarrhoea. Lively. Did, however, eat at 
noon. Albumen in the urine. 

March 14 — 11 o'clock — 1.0 through stomach tube. 
Trying to vomit. Until 3 o'clock in the after- 
noon, however, no vomiting. 

March 15 — Is found dead in the cage. Dissection ac- 
cidentally neglected. 

Experiment II. 
Dog of 5700 gr. 

March 22 — 1 gr. through tube. 

^' 23 — Was delivered of five living young ones. 

*' 24-29 — Dog and its young ones lively. 
That Martins yellow acts poisonous in stomachical 
application appears from Experiment I, as any another 
cause of death except the one through poisoning ap- 
pears to be excluded. 



72 COAL TAR COLORS IN FOOD PRODUCTS. 

Better proofs, however, are the following experi- 
ments in which the color was applied hypodermically. 

Experiment III. 
Dog of 5800 gr. 

April 30 — 10 A. M. — About 0.1 gr. in about 25 water 
injected hypodermically in several places of the 
back. Animal lively. In the afternoon diarrhoea. 

Mav 1 — 0.1 Hypodermic injection. ) y.. , 
May 2—0.1 '' '' | Uiarrnoea. 

Urine contains considerable albumen. When 
adding a little acid, a precipitate of free Dini- 
trophenol is produced. Ether added is colored 
weakly yellow. Addition of alkali to the separ- 
ated ether extract colors same and the alkaline 
solution yellowish brown. It is possible to color 
wool yellowish brown with the urine made 
weakly acidulous. 

May 3 — 0.1 hypodermic injection. 

May 4 — 0.15 hypodermic injection. The urine con- 
tains much albumen. The wool coloring suc- 
ceeds very well. This experiment proves that if 
small doses of Martins yellow are applied hypo- 
dermically, albuminuria is produced. 

Experiment VI. 

Dog of 8800 gr. 

April 30 — 0.1 hypodermic injection. 
May 1 — 0.1 hypodermic injection. 
May 2 — 0,1 hypodermic injection. Animal is exceed- 
ingly thirsty. 



NITRO COLORS. 73 

May 3 — 0.1 hypodermic injection. Thirst, Very 

little appetite. 
May 4 — 10 o'clock — 0.2 hypodermic injection. Urine 
dark brown. Contains albumen. Wool coloring 
successful. 

4 p. M. — Six hours after the injection heavy 
Dyspnoea. Very thirsty. 

7 P. M. — Animal completely apathetic. Strong- 
est Dyspnoea. 
The animal dies on the night of the 4th-5th of May. 
Dissection — Venous hypersemia of the rectum, of 
the liver, of the spleen, kidneys and lungs. Pneu- 
monia has begun. Intestines and skin not colored. 

This experiment is proof beyond contradiction. 
Only the poison could be the cause of death, as the 
operation — hypodermic injection — disappears as causa 
mortis. 

The animal received in the course of five days only 
0.6 gr. Martius yellow as Na. salt, or only 0.07 gr. 
per kilo. The poisoning with Martius yellow produces 
the following symptoms : 

Through the stomach it produces vomiting. The 
animals become very thirsty and develop high fever 
with pronounced Dyspnoea. After the first dose al- 
ready appears albuminuria. The animals die and as 
it appears mostly asphyctic. 

If the substance is brought directly into the blood 
(Cazeneuve Sc Lepine) or if it is injected under the 
skin, the same symptoms, with the exception of vomit- 
ing, are observed. 

The Martius yellow, therefore, belongs to the harm- 
ful colors. As coloring matter for food and liquid 



74: COAL TAR COLORS IN FOOD PRODUCTS. 

products at least it ought to be prohibited. For color- 
ing of fabrics which come in contact with the skin, 
its use is not advisable, as the same might prove 
harmful and dangerous to a scratch of the skin, even 
if it should only be very slight. 

The experiments in which the animals died or be- 
came sick when they received an injection of Martins 
yellow either in the blood or under the skin prove this 
absolutely. 

The fed Martins yellow is at least partly expelled 
unchanged through the urine. 

The wool coloring produced with the urine of the 
dog — presumably through admixture of the color of 
the urine — a somewhat darker shade than could be ex- 
pected of the pure Martins yellow. 

4. Naphthol Yellow S. 
C10H4N, OsSNa^ 

Naphthol Yellow S also called Acid Yellow S, fast 
yellow, aniline yellow, Succinine, sulphur yellow, Cit- 
ronine, Jaune nouveau, Jaune solide, is the calcium 
salt (natron or ammon.) of the Dinitro-a-naphthol 
sulpho acid. 

1. Dusted in concentrated sulphuric acid appears 
greenish yellow. The solution in sulphuric acid re- 
mains clear if diluted with water. Ether added to 
this solution remains colorless even upon addition of 
alkali, because the free color is insoluble in ether. 
Through this ether experiment Martins yellow which, 
on account of its cheapness is occasionally mixed with 
the Naphthol yellow S, can be easily determined. 



NITRO COLORS. 75 

2. The watery solution is not precipitated through 
muriatic acid. 

3. The watery solution does not produce a precipi- 
tate with liquor sodse. 

4. As in all nitro colored stuffs — cyanide of potas- 
sium produces a color resembling Isopurpuric acid. 

5. The watery solution even when diluted consider- 
ably is precipitated by ammoniacal copper solution. 
The solution of the crystalline precipitate in hot water 
remains clear upon addition of strong muriatic acid, 
and does not impart anything to ether. 

6. Muriatic acid solution of stannous chloride 
creates upon addition of : 

a. Ammonia, orange coloring. 

b. Ferric chloride, red coloring. 

7. Ferric chloride produces a Burgundy red precipi- 
pate which is partly dissolved when heated; reappears, 
however, when cooled off. 

Used in place of Picric acid for coloring of wool 
and silk and for printing of textile fibers. Also for 
coloring of food products ? 

Animal Tests. 
Cazaneuve and Lepine gave daily to a dog of 15 
kilos during 14 days 0.5 gr. Naphthol yellow S, then 
for ten days daily 2 gr. each and finally for 10 days 
4 gr. each. The animal was delivered of nine young 
ones. Eight of them lived. No disturbance whatso- 
ever was observed on the animal used for this 
experiment. The urine was free of albumen. Several 



76 COAL TAR COLORS IN FOOD PRODUCTS. 

times the color solution was injected directly into the 
blood. No symptoms of poisoning could be observed. 

2 to 4 gr. of the coloring (per kilo) produced in the 
human being colics and diarrhoea. 

The above named authorities consider the coloring 
matter as non-poisonous and as a weak purgative. 

Cazeneuve and Lepine curiously pronounce the naph- 
thol yellow (Jaune N. S.) used by them especially 
hard to dissolve, possibly they experimented with a 
different product. 

My own experiments were made on dogs with a 
preparation for which I am indebted to Dr. C. A. 
Schulz. Same was purified through extracting and 
re-crystallizing. 

Experiment I. 

Dog of 4800 gr. 

May 7 — 2 gr. dissolved in water through stomach 
tube. 

'' 8 — Did eat. Breathes quietly. Consistent 

almost black faeces. Urine neutral. 
Free of albumen. The coloring of wool 
succeeds. 1.75 gr. through stomach 
tube. 

'' 9-10 — No albumen in the urine. Animal lively. 
Breathes quietly. Ate well. No injec- 
tion. 

'' 11th — 2 gr. injected. Animal * normal. Traces 
of albumen in the urine (?). 

" 12th — 2 gr. injected. Animal normal. Traces 

of albumen in the urine. Solid faeces. 

In spite of the at least considerable dose of 7.75 gr. 



NITRO COLORS. 77 

in 6 days and 1.6 gr. per kilo animal, no poisoning 
symptoms with the exception of a very small albumi 
nurie which was probably there before the be- 
ginning of the experiment, were observed. 

The following experiments to which a female dog 
and her 3 1/2 weeks' old young one were used show 
that no poisoning symptoms appeared by hypodermic 
injection of naphthol yellow S. 

Experiment II. 

Dog of 5800 gr. 

May 11th — 0.2 gr. in about 32 ccm. water hypo- 
dermic injection. Animal lively and 
with good appetite. 
May 12th — 0.2 gr. hypodermic injection. 
"' 13th-16th — Animal lively. Desire to eat same as 

usual. Nurses its young one. 

Experiment III. 

3 1/2 weeks' old dog of 1040 gr. 

May 11th — 0.1 in about 15 water hypodermic injec- 
tion. 
** 12th — 0.1 hypodermic injection. Animal lively, 

also during the following days. 
Especially Test III shows that repeated doses of 
0.1 per kilo can be endured even by a hypodermic 
injection by a young animal, without producing any 
apparent disturbances. 

The harmlessness of naphthol yellow S is a still 
more interesting fact as the same differs from the 
very poisonous Martins yellow only through a sulpho 



78 COAL TAR COLORS IN FOOD PRODUCTS. 

group (HSO3). The H S O3 group, however, pro- 
duces the sohibility of the color. A soluble color, 
however, common sense teaches, should be more 
poisonous than the insoluble color, Martius yellow, 
from which it was obtained. We are plainly not as 
yet in a condition to decide about the poisonousness or 
non-poisonousness of a product except through ex- 
periments, no matter how well we know the chemical 
composition of the product. 

5. Brilliant Yellow. 
C10H3N, OsSNa. 

1. The aqueous solution colored yellowish brown is 
turned into a lighter yellow through muriatic acid but 
is not precipitated. Ether, if added, is colored pale 
yellow. 

2. Liquor sodae produces an orange yellow crystal- 
line precipitate. 

3. With ferric chloride the solution is colored a 
dirty yellowish green. In a striking light it is not 
transparent, almost black. Before the beginning of 
the dark coloring the solution appears for a short 
time colored reddish brown. 

4. Ammoniacal copper solution produces only after 
some time a crystalline precipitate. 

5. With stannous chloride and following the ad- 
dition of ammonia or ferric chloride, furthermore 
with cyanide of potassium, brilliant yellow acts the 
same as Martius yellow. 



nitro colors. 79 

Animal Tests. 

a. Stomacliical Application. 

Dog of 5650 gr. 

July 26th — Urine contains traces of albumen. 

'* 26th — 3 gr. in a little water applied through 
stomach tube. 

July 27th — Animal lively. Did eat. Urine intensely 
orange yellow. The coloring of wool through 
the urine, made weakly acidulous by sulphuric 
acid, succeeds. Urine contains brilliant yellow 
and doubtful traces of albumen. Urine mixed 
with muriatic acid imparts to ether a substance, 
coloring the ether a faint yellow. Liquor sodse 
discolors the ether almost completely, and be- 
comes itself yellow colored. 

July 28th — Animal lively. Did eat. Urine contains 
very little coloring matter. 3 gr. through tube 
dissolved in a little peptone. 

July 29th — Animal very lively. Urine almost free of 
albumen. Contains a great deal of coloring 
matter. Wool coloring succeeds well. 

July 30th — 2.5 gr. in a little peptone solution through 
tube. Urine alkaline. Almost free of albumen. 
Animal lively. Did eat. Coloring of wool in 
the urine, to which sulphuric acid was added, 
succeeds well. 

July 31st — 3 gr. through tube in a little peptone solu- 
tion. 

August 5th — Dog completely normal. Gained about 
180 gr. during the experimental period. The 
existence of the brilliant yellow in the urine was 



80 COAL TAR COLORS IN FOOD PRODUCTS. 

proven besides, through the coloring of the wool 
in the sulphuric acid bath, in the following man- 
ner : The urine is made acidulous with muriatic 
acid and shaken with ether. The ether extract 
imparts the coloring matter, liquor sodse, which 
is identified by the above described reaction. 

b. Hypodermic Injection. 

Dog of 11600 gr. 

July 27th — Urine free of albumen and sugar. 

'' 28th — 0.2 gr. brilliant yellow, suspended in about 
10 ccm. water. 
July 2 9 til — Urine in thin layers intensely orange yel- 
low; in thicker layers orange red, but free of 
blood and albumen. Animal lively. Did eat. 
July 30th — 0.3 gr. hypodermic injection. Animal 
lively. Did eat. Urine contains a little albu- 
men. 
July 31st — No urine. Animal lively. Did eat. 
August 5th — Dog is lively. Its urine contains very 
little albumen. It gained almost 300 gr. during 
the experimental period. 
I regret that I have no material for further animal 
experiments. 

The brilliant yellow applied through the stomach is 
surel}^ not poisonous, even in large doses. 

The dog which received the coloring matter in, com- 
paratively speaking, large quantities through hypo- 
dermic injections, was still completely lively for eight 
days after the last injection, and with good appetite. 
The secretion of albumen during the applications 



NITRO COLORS. 81 

remained exceedingly minimal. In brilliant yellow, 
the same as in naphthol yellow S, the ability of the 
sulpho group (H SO3) to make the product non-poison- 
ous is apparent. 

6. Aurantia. 
C12 Hs Ns O12. 

Aurantia or Kaiser yellow is the ammonium or the 
sodium salt of the Hexamitrodiphenylamin. 

1. Dusted in concentrated sulphuric acid is faintly 
yellow, addition of water produces flaky precipitate. 

2. Solutions of aurantia are precipitated by strong 
muriatic acid, at the same time discharging the free 
color acids. Ether dissolves the precipitate with yel- 
low color. If an alkali is added to ether it is dis- 
colored, the alkali is colored yellowish brown, almost 
red. 

3. No precipitate is produced through liquor sodae. 

4. Ammoniacal copper solution produces a vermilion 
red precipitate. When treated with fuming muriatic 
acid this produces a precipitate which acts the same 
with ether as described above under No. 2. 

5 . With cyanide of potassium, with muriatic solu- 
tion of stannous chloride, and with later addition of 
ammonia or ferric chloride, aurantia acts the same as 
nitro colors. Compare, however, picric acid. 

6. Ferric chloride produces a chamois colored pre- 
cipitate. It is used for orange coloring of wool, silk 
and especially leather. 

The poisonousness of aurantia has been repeatedly 
asserted and disputed. 



82 COAL TAR COLORS IN FOOD PRODUCTS. 

According to Gnehm, the preparation of Bindsch el- 
der and Busch, is poisonous. It produces blisters with 
considerable swelling upon the hands and arms of the 
workingmen engaged in the production of the color, 
and also of the dyers who use same. 

8. Summary. 

The results of the experiments which have been 
obtained in regard to the effect of nitro colors upon 
the animal organism warrant the following con- 
clusion : 

Only the sulphonized nitro dyes, naphthol yellow 
and brilliant yellow, are non-poisonous, and may be 
used for coloring of food and liquid products. 

Poisonous, however, are picric acid, Dinitrokresol 
(Saffronsurrogate) and Martins yellow. 

Suspicious, aurantia. 



AZO COLORS. 



Regarding the influence of some azo colors upon 
the human system as well as upon animals we are 
indebted to Cazeneuve & Lepine for some excellent 
tests which the following table will explain : 



AZO COLORS. 



83 



French Descrip 
tion. 



Rouge Soluble. 



Rouge Pourpre, 



Bordeaux B. 



Ponceau R. 



Orange I. 



Jaune Solide. 



Synonyms. 



Azorubin S, 

Fast Red, C. 

Carmoisin, 



Neucoccin, 
Brilliant- 
Ponceau, 
Cochineal Red 
or Fast R(?d 
D., Bordeaux 
8., Amaranth, 
Azo acid 
rubin 2B. 

Fast Red B, 



Ponceau 2R. 

Xylidin Red, 

Xylidin 

Ponceau. 



a Naphthol 
Orange 
Tropae(jlin 
OOU No. 1. 



Fast yellow 

R, Acid 

Yellow R, 

Yellow W. 



Constitution. 



C H^^^3^^ 
^0 6^N=.N-a.H.«^H 



'lO'^-^b 



aSO.sNa 



Q jj aSO. Na 

10 6^=N_c H (SOgNa) 

10 ViOH 

N. B. — Cazeneuve does not 
state which i?-Naphthol - di 
sulpho acid was used for the 
production of color. 



C HaN = N-C H^Q^^ . 

10 7 10 4(S0 iSia) 



C h/^^P2 ^oTT 

6 3T^_-i^__n XT POH 

^--^ ^io^4(SOgNa)^ 



C H (4) S^3^^ 



6 4 



(1) N=N-C^^Hg(a)OH 



(2)CH 



(2) CH 



C H SO Na 
6 3 3 4 "iNH 

(?) 

See Eger, Ber. 23,851, 188i). 






Mona- 

zo 
colors 



do. 



do. 



do. 



do. 



do. 



Effects. 



Non - poison- 
ous also for 
the human 
being. 



do. 



do. 



Non - poison- 
ous for dogs 

through stom- 
ach and also 

through blood 



do. 



For dogs 

through 

stomach and 

through blood 

harmless. For 

the human 
being harmful 
(.V 



84 COAL TAR COLORS IN FOOD PRODUCTS. 

The azo colors examined up to now belong, there- 
fore, entirely to the monazo colors, and are all en- 
tirely harmless. 

1. Bismarck Brown. 

Synonyms : Manchester brown, Phenylen brown, 
Vesuvin, Aniline brown, Leather brown. Cinnamon 
brown, Canelle, English brown and Gold brown. 

A dark brown powder, soluble in water, with a 
brown color. 

The aqueous solution produces : 

With muriatic acid a brown precipitate, soluble in 
water, with a brown color. 

With acetic acid, a brown solution, no precipitate. 

With liquor sodae, a brown precipitate, very little 
soluble in water. 

With ammonia, brown precipitate, which is soluble 
with brown color in excess of ammonia. 

With ammoniacal copper solution, brown precipi- 
tate hard to dissolve, even in hot water, reappearing 
in cooling off. 

a. Feeding Tests. 

Dog 1—5690 gr. 

June 11th — No albumen. 
June 12th — No albumen. 
June 13th — 2 gr. through tube. 

10:30— Injection. 

12:00 — Vomiting. 



AZO COLORS. 85 

June 14th — 2 gr. 

10:00— Injection. 

12:00 — Vomiting. Did not eat any- 
thing. 

June 15th — Did not eat anything. Animal moves 
about very little. 

June 16th — 2 gr. Two hours after injection violent 
vomiting. 

June I7th-20th — Did not eat anything. Drank only 
water. 

June 21st — Did eat. Livelier. Albumen in urine. 

June 22nd — 5 gr. Animal vomits J hour after injec- 
tion. 

June 23rd-27th — Did hardly eat anything. Albumen 
in urine. 

June 28th — Lively. 

June 30th — Did eat. Albumen in the urine. 

The animal was watched up to July 15tli. In the 

urine at the last only slight traces of albumen. Ap- 
petite as before. 

Dog IL— 29.5 kilos. 

April 29th — Little albumen. 
April 30th — 5 gr. through tube. 

May 1st — Urine brown. Animal lively. Eats as 

usual. 
May 2nd — 5 gr. through tube. Bismarck brown can 

be proven through wool coloring and through 

chemical reactions in the urine. 
May 4th — 5 gr. Urine brownish. No albumen. 
May 5th — Urine colored normal. No albumen. 



86 COAL TAR COLORS IN FOOD PRODUCTS. 

May 8 th — 15 gr. Animal vomited an hour after in- 
jection. 

May 9 th — Did not eat anything. Bismarck brown 
can be proven in the urine. 

May 11th — 15 gr. Vomiting one hour after injec- 
tion. 

May 12th — Animal eats little. Seems sick. 

May 14th — Animal lively again. 

May 15th — 15 gr. Vomiting 1^ hours after injec- 
tion. 

May 16th — Did not eat anything. Urine free of al- 
bumen. 

May 18th — Animal again normal. 

May 22nd — Animal normal. Weight, 28.9 kilos. 

Experiment III. 

Dog of 5.5 kilos received daily during a month 
0.25 gr. Bismarck brown with its food. The animal 
felt well during the whole time. Did not vomit and 
ate as usual. It gained during the experiment about 
350 gr. 

b. Hypodermic intra-abdominal injection. 

Test VI. 

Dog of 6.3 kilo received in the course of 20 days 
nine injections of 0.1 gr. Bismarck brown in 8 to 
10 ccm. sterilized water under the skin of the back. 
The animal remained absolutely normal. The urine 
was of normal color and did not contain any albumen. 

Test V. 

I injected 3 times each 0.1 grain Bismarck brown 
dissolved in 8 to 10 ccm. sterilized water in the ab- 



AZO COLORS. 87 

domen of the same animal. The animal showed a 
little rise of temperature and did not eat. Urine re- 
mained colorless. The dog recuperated completely 
within eight days. 

Bismarck brown produced vomiting and albumin- 
urie when administered through the stomach in dogs 
in a dose of 0.35 per kilo (Experiment I). Further 
disturbances did not set in even in large doses (Ex- 
periment II). Small doses (0.045 gr. per kilo) proved, 
even by frequent appHcation (Experiment III), entirely 
harmless. Hypodermical injections of doses of 0.016 
gr. (Test IV) proved harmless. The same doses, 
however, in abdominal injections produced light dis- 
turbances (Test V). 

The urine remained colorless in small doses. Only 
in larger dozes unchanged Bismarck brown could be 
proven in the urine. 

2. Sudan I. 

Sudan I. was first obtained from C. Lieberman out 
of the Diazobenzol chloride and /^-Naphthol. 

In its pure state red crystals. Not soluble in water. 
Soluble in alcohol with orange red color. 

The alcoholic solution produces : 

With liquor sodae, a red brown solution. 

With ammoniacal copper solution, a brown precipi- 
tate. 

With diluted ammonia, same as diluted liquor sodse. 

By dusting in concentrated sulphuric acid, fuchsine 
red solution which, upon diluting with water, pro- 
duces an orange yellow sediment. 



88 COAL TAR COLORS IN FOOD PRODUCTS. 

Dog I.— 11.9 kilos. 

June 7th — Urine alkaline. No albumen. 

June 8th — 2 gr. through tube. 

June 9th — No injection. Urine of normal coloring. 
Alkaline. No albumen. Dissolves a great deal of 
copper oxide in alkaline solution. Considerable 
sulphates. Distillate of the urine treated with 
concentrated muriatic acid produces a distinct 
sediment with bromine water. 

June 10th — No injection. 

June 11th — 2 gr. through tube. Dog lively. Hard 
faeces. 

June 12th — Did vomit. Otherwise lively. Urine is 
almost free of phenol. 2 gr. through tube. 

June 13th — 2 gr. through tube. Urine dark brown. 
Alkaline. Albumen plainly discernible. There 
are some sulphates. 

June 14th — 2 gr. through tube. Albumen distinct. 

June 15th — 2 gr. through tube. 

June 16th — Lively. Did eat. Weight 11.66 kilos. 
Lost 350 gr. in 10 days. 

June 22nd — Lively. Urine colored normal. No albu- 
men. 

June 23rd — 5 gr. through tube. Urine a little darker 
than normal. 

June 24th — Did eat little. 

June 25th — 5 gr. through tube. Ate little. 

June 26th — Through hot alcohol a great deal of un- 
changed coloring matter can be extracted out of 
the faeces which is again precipitated in red crys- 
tals when the alcohol is cooled off, and sbows the 



AZO COLORS. 89 

above described re-actions. Very little albumen 

in the urine. 
June 27th — Animal lively. Ate little. 
June 29th — Ate vs^ell. Urine colorless. 
June 30th — Animal lively. Very little albumen in the 

urine. 

The coloring matter is not entirely harmless in the 
administered doses, as it seems to be capable of pro- 
ducing some albuminurie. Hypodermic injections had 
to be omitted on account of lack of proper solvents. 

3. Metanitrazotin. 

Azo coloring matter of Diazo ilf-Nitraniline and 
combination with /^-Naphthol Cie H3 N3 O3 . 

The product is hardly soluble in alcohol of 90%. 
Very hard to dissolve in benzol and in glacial acetic 
acid. Soluble in v^arm alcoholic solution of caustic 
soda and is precipitated after filtration v^ith muriatic 
acid. The precipitate is washed out with hot water 
after decanting. The coloring matter presents a red 
powder. 

The alcoholic solution gives : 

With liquor sodse, Burgundy red coloring 
which is changed into yellow by acids. 
With ammonia as with liquor sodse. 

In dusting in concentrated sulphuric acid fuschine 
red liquid is produced which through diluting with 
water is colored orange yellow and shows a greenish 
yellow fluorescence ( through a finely distributed sedi- 
ment ? ). 



90 COAL TAR COLORS IN FOOD PRODUCTS. 

Dog I.— 12.6 kilos. 

July 11th — Traces of albumen in the urine. 

July 12 th — Same. 

July 12 th — 1 gr. through tube. Urine pale, alkaline. 
Traces of albumen. Phenol hardly to be proven. 

July 13th — 2 gr. through tube. Urine plentiful. Pale 
yellow. Cloudy. Considerably alkaline. By addi- 
tion of acids to the urine same effervesces consid- 
erably. No sugar. Traces of albumen. No phenol. 

July 14th — 2 gr. through tube. Urine considerably 
alkaline. 

July 15th — 2 gr. through tube. Urine very plentiful. 

July 16th — Dog lively. Weight 12.45. Lost, there- 
fore, 150 gr. within 5 days. 

A second dog (5.6 kilos) received 10 doses each one 
1 gr. in the course of 20 days. The animal kept well. 
The urine was free of albumen and colorless. Dura- 
tion of observation five weeks. 

After the experience gained with the nitro coloring 
matters I had counted upon a poisonous effect of the 
metanitrazotin. However, in spite of the presence of 
the nitro group, the color proved non-poisonous. 

4. Paraniirazotin. 
Azo coloring matter^out of Diazo p-Nitraniline and 
combination with y^-Naphtholmonosulpho acid S 
(Schaeffer) Ci6 Hg Ng Oe S Na. 

Keddish brown powder, soluble in water with an 
orange brown color. 

The watery solution gives : 

With liquor sodsB fuchsine red solution. 
With ammonia as with liquor sodse. 



AZO COLORS. 91 

With sulphate of copper no change. 
With ammoniacal copper solution, reddish 
violet sediment, soluble in ammonia with same 
color. 
If dusted in concentrated sulphuric acid a light red 
solution is produced which is colored orange yellow if 
diluted with water. The coloring matter, on account 
of its production, may be called Paranitrazotin. 

A rabbit of 1.5 ko. received two doses of 2.5 gr. each 
through the stomach tube in the course of three days. 
The animal remained well. 

Further experiments could not be undertaken on ac- 
count of scarcity of substance. 

5. Orange II. 
Ci6 Hn Ns O4 S Na. 
Synonyms : — Orange No. 2, /^-Naphthol Orange, 
Tropseolin 000 No. 2, Mandarin, Mandarin G Extra, 
Chrysaurin, Gold Orange. 

Orange red crystals easily soluble in water with 
orange red color. 

The aqueous solution produces : 

With muriatic acid, a brown precipitate, 
which is readily soluble in alcohol with orange 
red color. 

With liquor sodse, red brown solution. 
With ammonia as with liquor sodse. 
With ammoniacal copper solution, gelatinous 
red brown precipitate. 
By dusting in concentrated sulphuric acid, fuschine 
red solution which produces brownish yellow precipi- 
tate if diluted with water. 



92 COAL TAR COLORS IN FOOD PRODUCTS. 

a. Stomachical Application. 
Test I. — Black poodle of 10.5 kilos. 

July 4th — 5 gr. through tube. Urine red. DiarrhcBa ? 
Vomiting ? The red color of the urine fades out 
when heated with stannous chloride and muriatic 
acid. 

July 5th — No injection. Urine red through azo color- 
ing material. Vomiting (?). 

July 6th — Urine red. 

July 7th — Urine a little reddish, precipitating con- 
siderably. 

July 8th — Urine scarce, sediment considerable. 

July 9th- 12th — Urine alkaline, cloudy, contains al- 
bumen. 

July 13th — 7 gr. through tube. 

July 14th — Urine orange red. Did not eat anything. 
Diarrhoea. No injection. 

July 15th — No injection. Animal ate little. Urine 
a little reddish. 

July 17th — 2 gr. through tube. Did not eat anything. 
Diarrhoea. Urine neutral, a little reddish, very 
cloudy. Traces of albumen (?). 

July 18th — Animal very weak. Urine orange. Eyes 
closed by pus. 

July 19th — No injection. Animal miserable. 

Jul}^ 20th — Great deal of albumen in orange -colored 
urine. Animal very wretched. 40 degrees in 
recto. 

July 21st — Stridor in breathing. Cotton becomes 
orange-colored through urine. 

July 22nd — Animal very weak. Urine orange red. 



AZO COLORS. 93 

With NaOH dark red. With acids yellowish. 
Cotton dyeing succeeded well. 

July 23rd — Animal found dead in its cage. 

Dissection (July 24th) — Plenty fatty tissues of normal 
color. Muscles colored normal. Stomach and 
intestines pale. In the stomach and in the upper 
parts of the intestines were found many fresh 
and already cicratizing abscesses. The liver some- 
what fatty degenerated. Kidneys pale. Epithelium 
fatty degenerated. Lungs normal. Heart pale. 
Large white coagula in the heart. Brains color- 
less. 

Test II. 

A white rabbit, of 2.25 kilos, died after administer- 
ing of three gr. of the coloring matter within twelve 
hours. Four hours after injection the animal still 
jumped about lively in the room. Dissection was 
accidentally frustrated. 

b. Hypodermic Injection. 
Dog of 4300 gr. 

Dec. 12th — 0.5 gr. in about 10 ccm. luke warm water 

injected under the skin of the back (right). 
Dec. 12th-14th — Urine alkaline. A little albumen. 

No sugar. A little orange-colored. 
Dec. loth — No abscess at the place of injection. Lively. 

Did eat. 0.25 gr. hypodermic injection (back left). 

Urine orange red, acidulous. Traces of albumen. 

Wool dyeing in the urine made acidulous with a 

little sulphuric acid succeeds well. 



94 COAL TAR COLORS IN FOOD PRODUCTS. 

Dec. I7th — 0.5 hypodermic injection. No abscesses. 

A little diarrhoea. 
Dec. 18th — T = 39.5 degrees in recto. Right eye closed 

by pus and inflamed. Traces of albumen. Urine 

colored deep orange. Wool dyeing in urine was 

successful. No injection. 
Dec. 19th — Catarrh of the eyes is better, but cataract. 

0.5 hypodermic injection. Urine red orange. 

Animal lively. Solid fseces. 
Dec. 20th — No injection. Little albumen. Animal 

trembles. 
Dec. 21st — Solid faeces. Little albumen in the urine. 

0.75 gr. hypodermically injected in two places of 

the back. 
Dec. 22nd — Dog very wretched. Trembles a great deal 

and growls. Solid faeces. Little albumen in the 

urine. 
Dec. 23rd — Status idem. 

Dec. 25th — Abscess in place where injection of Decem- 
ber 21st was made. 
Dec. 26th — Livelier. 
Dec. 27th — Abscess opens by itself. Weight 3840 gr. 

Decrease in 15 days 460 gr. 
Jan. 2/89 — Abscess almost healed. Animal lively. 

Did eat. 
Jan. 3rd — Animal loses its hair. 
Jan. 14th — Animal almost without hair. Weight 

3890 gr. Lively. Eats considerably. 
Jan. 17th — Sleeps much. Eats considerably. 
Jan. 26th — Has recuperated completely. Weight 

5120 gr. 



AZO COLORS. 95 

/?-Naphthol orange, as shown by experiment I, is, 
even in small doses, poisonous through the stomach, 
and brought about the death of a medium sized dog; 
as specific may be considered the experiment with the 
rabbit (II). 

In contrast to /^-Naphthol orange, Cazeneuve and 
Lepine found the corresponding a-naphthol orange to 
consist probably of: 




HSO3 

which varies from y^-Naphthol orange only through 
the position of the Hydroxy 1 group to be non-poisonous. 
Even in hypodermic injections the ^ coloring matter 
seems to produce poisonous effects. The animal, how- 
ever, withstood the attack. 

6. Ponceau 1^ G, B, 
CieHiiNASNa. 

Synonyms — Crocein Orange, Brilliant Orange. 

A red powder, if strictly pure, crystalline, which 
does not dissolve easily in water with a red color. 

The watery solution gives : With muriatic acid, a 
yellowish brown precipitate which dissolves in alcohol 
easily, with a yellowish red color. 

With liquor sodse, a yellow solution. 

With ammonia, same as with liquor sodae. 



96 COAL TAR COLORS IN FOOD PRODUCTS. 

With ammoniacal copper solution, a dirty yellowish 
brown precipitate. 

By dusting in concentrated sulphuric acid, orange 
yellow solution which, if diluted with water, produces 
a yellowish brown precipitate. 

Dyes wool in acid bath orange-yellow. 
Dog I.— 12.4 kilos. 
June 19th — 2 gr. in water through tube. Urine rose 

colored. 
June 20th — 2 gr. in water. Urine reddish. 
June 21st — 2 gr. in water. Dog lively. Urine red- 
dish. No blood. No albumen. 
June 22nd — 2 gr. through tube. Dog lively. Urine 

alkaline. No albumen. No phenol. 
June 23rd — 4 gr. through tube. Urine normal colored, 

alkaline, cloudy. No albumen. 
June 24:th — Animal lively. Did eat. 
June 27th — 4 gr. through tube. 

June 28th — Urine normal colored. Free of albumen. 
In a second experiment a dog of 8.5 kilos received 
daily during one month one gr. of the coloring 
matter through tube. Urine remained colorless. The 
animal was lively. The appetite was not disturbed. 
The loss of weight — 200 gr. in thirty days — cannot be 
taken into consideration. 

This color can therefore be considered as non- 
poisonous. 

T. Orseille Substitute. 

Cie H,, N, 0, SNa 

Synonym : — Naphtion red (old). 
A brown paste soluble in water, with a reddish 
brown color. 



AZO COLORS. 97 

The watery solution gives : 

With muriatic acid, a bluish red precipitate soluble 
in water and 96% alcohol, with reddish brown color. 

With acetic acid, a reddish brown solution. 

With liquor sodse, bluish red precipitate, which is 
very little soluble in water; readily soluble in alcohol — 
with a brownish red color. 

With ammonia, brownish red solution. 

With ammoniacal copper solution, a dirty red pre- 
cipitate soluble in hot water. 

By dusting in concentrated sulphuric acid fuchsine 
red solution which precipitates upon addition of water 
a reddish brown sediment. 

Dyes wool in acid bath orseille red. 

a. Stomacliical Application. 

Dec. 24:th-28th— Dog of 3810 gr. Urine weakly, 
alkaline, contains a little albumen. No Mucin. 

Dec. 27th — 20 cm. Orseille solution (=1.64 gr. color- 
ing matter), with peptone, through tube. There- 
after inclination to vomit. Did not vomit. Urine 
normal colored, almost clear, weakly alkaline. 
Traces of albumen. With acids, alkalines and 
concentrated sulphuric acid no characteristic 
change. 

Dec. 28th — 20 ccm. orseille solution ( = 1.64 gr. color- 
ing matter), with peptone, through tube. Urine 
as on the 27th. Solid faeces. Lively. 

Dec. 29th — No injection. 

Dec. 30th — 40 ccm. orseille solution ( = 3.28 gr. color- 
ing matter). 



98 COAL TAR COLORS IN FOOD PRODUCTS. 

Dec. 31st — Lively. Did eat. Urine as usual. Weight, 
3.980 gr., therefore a gain of 170 gr. within 7 
days. 

Jan. 1/89 — Urine colorless. A trifle albumen. Plenty 
of sulphates. 

Jan. 2nd — 50 ccm. orseille solution ( = 4.1 ^r. coloring 
matter), with peptone, through tube. Urine 
alkaline. Otherwise as before. Colorless. 

Jan. 3rd — Urine dyes filtering paper rose color. 
Alkaline. Very little albumen. Wool dyeing 
successful in urine made acidulous. Animal 
lively. Discontinued. 

A second experiment, in which a dog of 4.5 kilos 
received daily during one month 10 ccm. dye stuff 
solution (0.82 gr. color), that is in total 30 times 0,8 
gr. = 24 gr. coloring matter, took the same course as 
Experiment 1, only the urine remained colorless. 

b. Hypodermic Injection. 
Dog of 4980 grams. 

Jan. 2nd — Urine colored normal. Very little albumen. 

10 ccm. orseille substitute solution hypodermic 

( = 0.82 gr. color). 
Jan. 3rd — Urine reddish. No injection. 
Jan. 4th — Urine reddish. Traces of albumen. 10 ccm. 

orseille substitute solution hypodermic ( = 0.82 gr. 

color) left of back. 
Jan. 5th — Urine reddish. Hardly any albumen. 

Plenty sulphates. Animal lively. No abscesses. 

No injection. 
Jan. 6th — No abscesses. Animal lively. Little al- 
bumen. 



AZO COLORS. 99 

Jan. 8th — Animal normal. Urine colorless. Little 
albumen. 

Jan. 9th — Animal did eat. No abscesses. 20 ccm. 
injection (=1.64 gr.) in two places of the back. 

Jan. 10th — Did not eat anything. Conjunctiva 
colorless. Urine reddish. Little albumen. No 
abscesses. No injection. 

Jan. 11th — No abscesses. Urine colorless. Little al- 
bumen. No injection. 

Jan. 12th — Urine colorless. Little albumen. 

Jan. 14th — Weight 4950 gr. No loss of weight 
within twelve days. Lively. No abscesses. 

Jan. 17th — Lively. Very little albumen. 

This coloring matter cannot be considered as poi- 
sonous in the described doses, neither through the 
stomach nor if injected hypodermically even though 
it contains a nitro group. Probably the effect of the 
NO^-group has been modified through the also present 
HSOa-group, similar as in Naphthol Yellow S. 

8. Chrysoidin. 
C^Hi^N^HCl. 
The watery solution produces : 

With muriatic acid, a gelatinous brown precipitate 
easily soluble in water with an orange brown color. 

With acetic acid, no change. 

With liquor sodae, orange brown precipitate which 
is hardly soluble in water, readily soluble in alcohol 
with an orange yellow color. 

With ammonia, same as with liquor sodse. 

With ammoniacal copper solution, a brownish red 

LofC. 



100 COAL TAR COLORS IN FOOD PRODUCTS. 

precipitate soluble in hot water, insoluble in alcohol. 
By dusting in concentrated sulphuric acid, yellowish 
brown solution which becomes ponceau colored when 
diluted with water. 

a. Stomachical Application. 

March 24:th-25th— Dog of 26.6 kilos. Urine not col- 
ored. Contains distinct albumen. 

March 25th-26th — 3 gr. through tube. 

March 26th-2Tth — Urine colored considerably orange 
brown. Urine contains distinct albumen. 

March 29th-30th — Urine little colored. Animal lively. 

April 1st — 10 gr. through tube. 

April 2nd-5th — Urine colored deep brown. Little 
albumen. 

April 6th-Tth — 10 gr. Chrysoidin. Animal did eat. 
Did not vomit. 

April 8tli-10th — Urine dark brown. Distinct al- 
bumen. 

In a second experiment a dog of 9.5 kilos received 
during one month daily one gr. of Chrysoidin through 
tube. The animal remained lively. Urine was col- 
orless and almost free of albumen. It lost during 
this time 1.2 kilos, about one-eighth the total 
weight. 

b. Hypodermic Injectio7i. 

April 12th — Dog of 5.85 kilos. Urine not colored. 
Traces of albumen. 

April 13th-14th — 0.1 hypodermic in 10 ccm. steril- 
ized water. 

April 15th-2Tth — Urine not colored. Little albumen. 
Animal lively. Eats as usual. 



AZO COLORS. 101 

April 29th-30th — 0.1 hypodermic injection. 

May 2nd-3d — Animal lively. Urine not colored. 

May 5th — Urine not colored. Very little albumen. 

May 8th — 0.1 hypodermic injection. 

May 10th — Urine normal. No abscesses. Ate 

well. Weight 4.620 gr. Loss 1.230 gr. This is 

more than ^ of the total weight. 
May 15th — Animal normal. Eats a great deal. Urine 

almost free of albumen. 

c. Injection into the Abdomen, 

A dog of 4.5 kilos received three times in the 
course of 10 days, 0.1 Chrysoidin in sterilized water 
by means of a sterilized syringe injected into the ab- 
domen. 

The urine remained colorless but contained a little 
albumen. The animal was still very lively more than 
three weeks after the end of the test and kept up a 
good appetite. 

The chrysoidin effects, as my tests show, a little 
albuminurie and causes a considerable loss of weight. 
Further disturbances were not observed. After large 
doses were applied to the stomach a part of the color- 
ing matter was taken up by the urine. 

Contrary to the experiments made with the dog, 
Blaschko describes a repeated recidivating eczema of 
a laborer engaged in the production of chrysoidin. 
Whether this skin disease was really produced through 
the chrysoidin or rather through the different ma- 
terials used for its production — especially Metaphenyl- 
endiamin seems suspicious — needs, I believe, fur- 
ther proofs. 



102 COAL TAR COLORS IN FOOD PRODUCTS. 

9. Diphenylariiine Orange. 
C18H14N OaSNa. 

Synonyms: — Acid yellow D., diphenyl orange, 
orange IV., tropseolin 00, orange B., Jaune d'ani- 
line, helioxanthin (?) orange G. S. , new yellow. 

Orange yellow powder not very easily soluble 
in cold water with orange red color. 

The watery solution yields : 

With muriatic acid, a reddish violet precipitate which 
is very little soluble in water producing violet solution, 
the precipitate is easily soluble in 96% alcohol with 
orange red color. 

With liquor sodse, egg yellow precipitate which is 
hardly soluble in water with egg yellow color ; solu- 
ble in 96% alcohol with orange red color. 

With ammonia, orange yellow precipitate, which is 
readily soluble in an excess of ammonia. 

With ammoniacal copper solution, yellow precipitate, 
which is soluble in hot water with a brown color, 
which, however, is precipitated again when cooling off. 

By dusting in concentrated suliDhuriic acid, a bluish 
violet solution which produces a violet sediment when 
diluted with water. This sediment is soluble in an 
excess of water with a reddish violet color. 

Dyes wool orange yellow in the acid bath. Serves 
as an indicator in titrating, as it is colored red through 
a little free acid (not through carbonic acid). 

a. Stomachical Application. 
Test I. 
Jan. 16-18th— Dog of 27.35 kilos. Little albumen. 
Jan. 19th — 5 gr. in peptone through tube. Urine, if 



AZO COLORS. 103 

allowed to stand, becomes dark colored from top 
downwards. Contains albumen. Considerable 
sulphates. Alkaline. Lively. Did eat. 

Jan. 20th — Urine almost black. Otherwise as on the 
19th. 

Jan. 21st — 5 gr. Urine alkaline. Almost black. The 
urine distilled with strong muriatic acid shows 
only traces of phenol. The genuine urine shows 
with ferric chloride no characteristic change. If 
treated with strong muriatic acid a flaky precipi- 
tate is produced which is not soluble in water, but 
soluble in hot alcohol. The filtrate of the urine 
precipitated with acid shows the distinct reactions 
of albumen. 

Jan. 23d — The precipitate produced through acid has 
disappeared out of the urine. Plenty of albumen. 
3 gr. 

Jan. 24:th — Precipitate produced by muriatic acid is 
missing. Urine almost colorless. Little albu- 
men. 

Jan. 25th — Urine very dark colored ; produces pre- 
cipitate with muriatic acid. Little albumen. 

Jan. 26th — Urine colorless. Little albumen. 

Jan. 27 — Same as on the 26th. 

Jan. 28th. — 10 gr. Considerable urine, almost black. 
Same contains much albumen and considerable 
sulphates. Alkaline. 

Jan. 29th-30th — Urine colored dark. Much albumen. 
Has eaten little. 

Jan. 31st — Plenty of ^albumen. Weight 26.35 kilos; 
therefore a loss of 1 kilo; that is, 1/27 part of the 
weight within 14 days. 



104 COAL TAR COLORS IN FOOD PRODUCTS. 

Feb. 2d — 15 gr. Urine colored deep black. Pientj 
albumen. Animal lively. 

Feb. 3d — Urine dark brown. Distinct traces of albu- 
men. Did eat well. 

Feb. 7th — Urine almost normal colored. Animal 
lively. 

Test II. 

Jan. 15th-18th— Dog of 9730 gr. Little albumen. 

'^ 19th — 3 gr. in peptone. 

'' 21st— 3 gr. 

** 22d — No injection. Animal lively. 

'' 23d— 2 gr. Did eat. 

*' 27th — Lively. Did eat. 3 gr. color. 

'' 28th-30th— Each 3 gr. color. Animal lively. 

*^ 31st — 3 gr. color. Animal did eat. Lively. 
Weight 9820 gr. 

The animal receives from February 2d to 15th daily 
three gr. coloring matter. In the urine unchanged 
coloring matter and albumen. Animal remains 
lively. 

b. Hypodermic Injection. 

Test III. 

March 20th — Dog of 5450 gr. Distinct albumen in 

the urine. 
March 21st-22d — Urine colorless. Contains distinct 

traces of albumen. 0.1 hypodermically. 
March 22d-23d — No abcess. Urine colorless. Animal 

lively. 
March 23d-24th — 0.1 hypodermically. No abscees. 

Urine colorless. Little albumen. 



AZO COLORS. 105 

March 25th-26th — Urine colorless. Little albumen. 

No change with muriatic acid or liquor sodae. 
March 26th-27th — No abscess. Did eat. 
March 29th-30th — No abscess. Urine colorless. 
March 31st-April 4th — Did eat. 0.1 hypodermic. 
April 4th — Lively. No abscess. Weight of the body 

5220 gr. ; therefore, a loss of 230 gr. ; that is, 1/24 

of the total weight in 14 days. 
April 12th — No abscess. Lively. 

The Diphenylamine orange therefore produces 
albuminuric, according to above tests. Further dis- 
turbances did not appear after observation of the 
animals used for the tests during several weeks. 

10. Metanil Yellotv. 
Ci8Hi4N303SNa. 

The coloring matter, a yellowish brown powder, 
smells strongly after diphenylamine. 

The aqueous yellow-colored solution produces with 
muriatic acid a violet precipitate which is gradually 
dissolved by an excess of muriatic acid or water into 
a f uchsine red liquid. Liquor sodse does not change the 
watery solution at first. After a little while, how- 
ever, a yellow crystalline precipitate is produced 
which is soluble in warm water with an orange red 
color. 

By dusting in concentrated sulphuric acid a violet 
solution is produced, which becomes colored f uchsine 
red if diluted with water. 

With ammoniacal copper solution a heavy, ocher 
yellow, flaky precipitate is produced, which is very 
hard to dissolve in water. 



106 COAL TAR COLORS IN FOOD PRODUCTS. 

For purifying purposes the coloring matter was 
dissolved in water, filtered and extracted by sodium 
acetate. After drawing off the yellow material is ob- 
tained in the shape of yellow crystals out of the hot 
alcohol in which it is hardly soluble at all. The color- 
ing matter used for the physiological experiments was 
almost pure, as is proven by the following analysis: 

0.4895 gr. of coloring matter dry at 105 degrees 
yielded 0.084 Nag SO4 

TVT Brown. Colored. 

JMa 

6.1 5.6 

Same as Diphenylamine orange dyes wool orange 
yellow in the acid bath. 

a. Stomachical Application. 
Test I. 

April 2nd — Dog of 11.600 gr. Urine almost free of 

albumen. 
April 4th-5th — 10 gr. Metanil yellow through tube. 

Animal vomited and did not eat anything. 
April 5th-6th — 10 gr. metanil yellow. Did vomit 

and did not eat anything. 
April 7th — Animal is very miserable. Did not eat 

anything. Respiration difficult. 
April 8th — Died during the night of 7th-8th. 

Dissection: — Stiff. Outer skin not colored. Mu- 
cous membranes yellowish. Intestines pale, not 
colored. Kidneys pale, not colored. Liver red, 
contains a great deal of unchanged coloring mat- 
ter, as it is colored red with concentrated sul- 
phuric acid. In the stomach a great deal of un- 



AZO COLORS. 107 

changed coloring matter. In the otherwise nor- 
mal lungs a circumscribed focus in which tuber- 
culosis bacilli can be proven. The deposit was 
found on the front part of the lower right lobe 
of the lung. 

The animal received in the course of 4 days 20 gr. 
of coloring matter, that is, l.T per kilo and was killed 
by this dose. 

Test II. 

March 19th- 2 0th— Animal of 11.25 kilos. Distinct 

traces of albumen. 
March 20th-21st — 1 gr. Urine colorless. Distinct 

traces of albumen. 
March 22nd-23rd — Urine colorless. Becomes colored 

dark from the top downwards. Distinct traces 

of albumen. 
March 21th-25th — Urine orange yellow in thin layers. 

With muriatic acid bluish violet. With liquor 

sodse orange red. Animal lively. Conjunctiva 

not colored. 
March 25th-26th — 10 gr. Dog vomited considerably 

about one hour after injection. 
March 26th-27th — Ate little. Urine dirty greenish 

yellow. 
March 28th-29th — Urine colored normal. Distinct 

traces of albumen. 
April 1st — 5 gr. Animal ate very little. Died dur- 
ing the night of lst-2nd of April. 8750 gr. 
Dissection: — Skin and subcutaneous cellular tissue, 
serose, intestines, contents of intestines yellow colored 
(metanil yellow). Contents of the intestines were 



108 COAL TAR COLORS IN FOOD PRODUCTS. 

colored ruby red with concentrated sulphuric acid, 
contained therefore unchanged coloring matter. Liver 
very rich on blood, colored dark red, re -action with 
concentrated sulphuric acid. Kidneys colored deep 
yellow. Conjunctiva yellow. Urine of the bladder 
orange yellow, becomes red through concentrated sul- 
phuric acid, therefore contains unchanged coloring 
matter. 

The dog received in the course of 12 days 21 gr. of 
coloring matter, therefore 0.53 gr. per kilo. This 
dose proved fatal. 

b. Hypodermic Injection. 

Test III. 

Dog of 5220 gr. 

April Srd-lth — Traces of albumen in the urine. 

*^ 5th-t)th — 0.1 gr. in 10 ccm. sterilized water 

hypodermically. Animal trembles a great deal. 
April 7th — Urine uncolored. No abscess. Animal 

trembles. 
April 9th — 0.15 gr. hypodermic injection in two 

places. Animal trembles, eats a great deal. 
April 11th — 0.15 gr. hypodermically. No abscess. 

Animal livelier, no more trembling observed. 

Urine not colored. Contains traces of albumen. 
April 14th — 4790 gr. Animal lively. Did eat. 

In accordance with tests I and II the metanil yel- 
low must therefore be considered poisonous through 
the stomach. The dosis lethalis proves to be 0.53 gr. 
according to test II. 

The isomeric diphenylamine orange, however, is 
non-poisonous . 



AZO COLORS. 109 

11. Azarin S. 

Yellowish orange colored thin paste. It smells 
after sulphuric acid and shows strong acid reaction. 
Not completely soluble in water. 

The watery solution yields : by heating with mu- 
riatic acid a yellow precipitate which is soluble in al- 
cohol with a yellow color. 

With ammonia, brownish red solution. 

With liquor sodse, bluish violet solution which be- 
comes reddish violet colored when heated and retains 
this color when cooling off. 

With concentrated sulphuric acid, dark, red solution, 
at the same time the sulphurous acid escapes. In di- 
luting the red solution with water, a brown precipi- 
tate is produced, which is readily soluble in alcohol 
with brown color. 

With ammoniacal copper solution, violet precipitate; 
in thin layers this precipitate appears red. 

a. Stomachical Application. 

A large dog of 25.6 kilos received in the course of 
25 days 35 gr. Azarin suspended in water through the 
tube. The urine was colored faintly yellow and con- 
tained distinct traces of albumen ; when heating same 
with muriatic acid, sulphurous acid was developed. 
The appetite of the dog was not diminished. 

In a second experiment a dog of 10.3 kilos received 
in the course of 20 days 20 gr. Azarin S. which were 
given him through the tube. Urine as in Test I. The 
animal remained lively. 



no COAL TAR COLORS IN FOOD PRODUCTS. 

b. Hypodermic Injection and Injection into the 

Abdomen. 

A dog of 4.7 kilos received injected under the skin 
of the back three times in the course of eight days, 
each time 0.1 gr. azarin paste mixed with 10 ccm. 
water. No abscesses appeared during the time of the 
observation (three weeks). No albumen. No strange 
coloring matter in the urine. Appetite undisturbed. 

Into the abdomen of another dog were injected with 
Koch's sterilized syringe on May 16th about 5 ccm. 
azarin paste dissolved in about 5 ccm. sterilized water — 
in total therefore about 10 ccm. liquid. The following 
day the animal did not eat anything. The urine re- 
mained colorless. On the third day the animal ap- 
peared to be very miserable. Did not eat anything. 
Trifle albumen in the urine. The following day the 
dog is found dead in its cage. 

Dissection. — Peritoneum and the surface of the in- 
testines are covered with red flakes of a coloring mat- 
ter. The small intestine considerably inter- grown with 
the peritoneum. 

Diagnosis. — Peritonitis, adhsesive, sicca. 

This product of the dissection is of considerable in- 
terest. The red flakes consisted, as the chemical 
analysis proved, of the azo coloring matter which is 
the foundation of azarin S. ; therefore the same process 
took place in the peritoneal cavity which takes place 
in flxing azarin on the tissue. 

Through the stomach azarin S. is harmless. 



DISAZO COLORS. 



Ill 



2. DISAZO COLORS- 

The Disazo coloring matters examined by me are 
classed in the following table : 



o 

a 

a 
a 

Pi 



Commercial 
Name. 



Fast 
Brown G. 

Wool Black, 



Naphthol 
Black P. 



Congo. 



Azo Blue. 



Chrysamin 
R. 



Peoduction. 



Diazotized 
Base. 



2 mol. Sul- 
f anil Acid. 

Amidoazo- 

benzoldi- 

sulpho acid. 

Amidoazo- 
naphtalindi- 
sulpho acid. 



Benzidin. 



o-Tolidin. 



o-Tolidin. 



Combined 
Wilh. 



a-Naplithol, 



p-Tolyl 

/5-Naplity- 

lamin. 

/^-Naphthol 

disulpho 

acid R. 



1 mol, m. 
Amidoben- 

zolsulpho 

acid 1 mol. 

Naphtion 

acid. 

2 mol. a- 
Naphtolmo- 

nosulpho 
acid N. W. 

2 mol. Sali- 
cylic acid. 



Group of the 
Disazo 
Colors. 



Primary. 



Secondary. 



do. 



Congo group 



do. 



do. 



Effects. 



Harmless. 



Harmless. 



Harmless 
through the 

stomach, 
harmful in 
hypoderm c 

injections. 

Harmless. 



Harmless. 



Harmless. 



1. Fast Brown G. 

C22 Hi4 N4 O7 Ss Nag 
Brown powder soluble in water with reddish brown 



color. 



112 COAL TAR COLORS IN FOOD PRODUCTS. 

The watery solution yields : With strong muratic 
acid, a violet precipitate soluble in excess of muriatic 
acid with violet color which is soluble in water with a 
brown color. 

With liquor sodse, cherry red solution. 

With ammonia as with liquor sodse. 

With ammoniacal copper solution, only in concen- 
trated solution a precipitate which is readily soluble in 
water with cherry red color. 

Dusted in concentrated sulphuric acid, a reddish vio- 
let solution which becomes brownish yellow colored 
when boiling. The reddish violet solution in concen- 
trated sulphuric acid is colored cherry red w^hen diluted 
with water. 

a Stomachical Application. 
Test I. 

Jan. 15th-18th — Dog of 9.630 gr. Urine contains 
very little albumen. 

Jan. 19th — 3 gr. of fast brown through tube. 
'^ 20th — Little albumen. Almost normal colored. 
Is colored bluish red with NaOH, therefore must 
contain traces of the applied coloring matter. The 
urine acidified with acetic acid dyes wool reddish 
brown. 

Jan. 21st — 3 gr. 

" 22d — Diarrhoea. Urine red, free of blood, little 
albumen, with NaOH bluish red. The dyeing of 
wool with the urine acidified with acetic acid suc- 
ceeds very well. 

Jan. 23d — Urine faintly colored, with NaOH faintly 
bluish red. 2 gr. 



DISAZO COLORS. 113 

Jan. 24th — Urine deeply red-colored. Little albumen. 
^^ 25th — Traces of albumen. Urine colorless. 
'^ 26th-29th — Urine colorless. Very little albumen. 
" 30th — Almost free of albumen. 5 gr. color. 
'^ 31st — Considerable diarrhoea. Urine hardly col- 
ored, turns faintly fuchsine red with NaOH. Lit- 
tle albumen. Weight, 8.820 gr. 
Feb. 3d— 10 gr. color. 
** 4th — Heavy Diarrhoea. Urine contains un- 
changed fast brown G. Did not eat. 
Feb. 5th — Urine as on the day before. 
'' Tth — Urine colorless. Very little albumen. 
Diarrhoea. Did eat a little. 
Feb. 12th — Animal normal. Little albumen in the 
urine. 

In a second test a dog of 5.6 kilos received daily for 
one month 2 gr. fast brown G. After the sixth dose 
light diarrhoea set in which continued almost through- 
out the entire month. The desire for eating decreased. 
Loss of weight about 1/5 of the total weight. 

According to these tests the coloring matter pro- 
duces diarrhoea in continued applications even in 
small doses (Test II), and in less frequent applications 
in larger doses (Test I) loss of appetite. Weight de- 
creased. 

b Hypodermic Injection. 

March lst-3d— Weight 6730 gr. 

'* 3d-4th— No albumen. 

*' 4th-5th — 0.1 gr. hypodermic injection in 10 
ccm. lukewarm water. Urine not colored. Lit- 
tle albumen. 



114 COAL TAR COLORS IN FOOD PRODUCTS. 

March 5th-6th — No abscess. Urine colorless. No al- 
bumen. 
March 6th-7th — No abscesses. 0.1 hypodermic. 
'* 7th-8th — Colorless. No abscess. No albu- 
men. 
March 7th-llth— As on the 7th-8th. 
'' llth-12th— 0.1 hypodermic. 
'' 12th-13th— No abscess. 

** 13th-14th — 0.1 hypodermic. Animal contin- 
ues to be lively. Did eat. 
March 14th-18th — No abscesses. Urine colorless. Lit- 
tle albumen. 
March 20th — Animal lively. Weight 6450 gr. 
** 23d — No abscess. 

*' 24th-25th — No abscess. Urine almost color- 
less. Little albumen. No change with NaOH 
or muriatic acid. 
March 25th-26th — 0.1 hypodermic. 

'^ 28th — Animal lively. Discontinued. 
April 10th — No abscesses. Animal lively. 

The health of the animal was not impaired through 
repeated doses of 0.1 gr. coloring matter injected hy- 
podermically. 

2. Wool Black. 

0^9 H21 N5 Oe S2 Na^ 

Black blue powder soluble in water with bluish vio- 
let color. The watery solution yields: With muriatic 
acid, reddish violet precipitate which is soluble in water 
with the same color. 

With liquor sodae, violet precipitate which is readily 
soluble in water with the same color. 



DISAZO COLORS. 115 

With ammonia, bluish violet solution. 

With ammoniacal copper solution, bluish violet pre- 
cipitate, which is very little soluble in water. 

By dusting in concentrated sulphuric acid, a blue 
solution is produced, which, when diluted with water, 
produces a brown precipitate, which is decomposed 
through boiling. 

Through boiling with diluted sulphuric acid, wool 
black is decomposed (according to Witt) into Tolu- 
naphtazine and Amidoazobenzoldisulpho acid. 

Wool black dyes wool bluish black in the acid bath. 

a. Stomacliical Application. 
Test I.— Dog of 29.94 ko. 

Dec. 26-27 — Urine a little alkaline. Contains some 
albumen. 

Dec. 2Sth — 5 gr. of wool black in peptone through 
tube. Urine of normal color, neutral, contains 
a little albumen, considerable sulphates, shows 
with acids, alkalines (even at a boiling point), 
concentrated sulphuric acid, ferric chloride, no 
characteristic changes. 

Dec. 29th — 5 gr. wool black. Lively. Faeces black. 
Urine normal colored. 

Dec. 30th — 5 gr. wool black. Lively. Urine nor- 
mal colored. Albumen and sulphates as before. 
Faeces, black, hard. 

Dec. 31st until Jan. 1st, 1889 — Urine not colored. 

Jan. 2nd — 10 gr. of wool black through tube. Urine 
intensely dark blue, in thick layer black, dyes 
wool blue black in acid bath. Urine contains 



116 COAL TAR COLORS IN FOOD PRODUCTS. 

albumen. Examined as to albumen after extract- 
ing of the dye acid and filtering. 

Jan. 4th — Urine colorless. Faeces blue. Little al- 
bumen in the urine. 10 gr. of wool black. 

Jan. 5 th — Urine intensely dark blue, in thick layer 
almost black. The coloring matter can be ex- 
tracted from the urine through sodium acetate. 

Jan. 6th-7th — Animal did eat. Urine colorless, be- 
comes dark from top downwards when standing. 
Alkaline. Albumen distinct. Sulphates plenti- 
ful. FsGces normal colored. 

Jan. 7th-12th — Animal lively. 

Jan. 13th-19th — Urine distinctly contains albumen. 
Animal lively. Eats well. 

Jan. 20th — Animal lively. Little albumen in the 
urine. 

b. Hypodermic Injection, 
Test II.— Dog of 3520 gr. 

Jan. 20th — Urine colorless. Free of albumen. 

Jan. 21st — 0.25 gr. wool black in 10 ccm. lukewarm 
water injected under the skin of the back. 

Jan. 22nd — Temperature 39.5 in recto. Urine color- I 
less. No abscess. Lively. Did eat. 

Jan. 23rd — 0.25 gr. Lively. No abscess. 

Jan. 24th — 0.25 gr. Urine not colored. Traces of 
albumen. 

Jan. 26th-27th — Urine colorless. Temperature nor- 
mal. 

Jan. 28th — Abscess on. right half of the back. 0.25 
gr. hypodermic. 

Jan. 29th — Urine colorless. Little albumen. 



DISAZO COLORS. ll'T 

Jan. 30th — Urine colorless. Alkaline. Little albu- 
men. Abscess has become smaller. 

Wool black is non-poisonous in stomachical applica- 
tion as well as in hypodermic injection. 

3. Naphthol Black P. 

C30 H16 N4 Oi3 S4 Na4. 

Bluish black powder soluble in water with dark 
bluish violet color. The watery solution yields: 

With muriatic acid, a bluish violet solution. 

With acetic acid, same as with muriatic acid. 

With liquor sodse, same as with muriatic acid. 

With ammonia, same as with muriatic acid. 

With ammoniacal copper solution, fuchsine red 
solution. No precipitate. 

With copper sulphate, as with ammoniacal copper 
solution. 

With barium chloride, bluish violet precipitate which 
is hard to dissolve in water. 

With ferric chloride, same as with barium chloride. 

B}^ dusting in concentrated sulphuric acid dirty 
green solution which is colored blue upon addition of 
water. 

a. Stomachical Application. 
Test I. 

March lst-2nd — Dog of 26.73 kilos. Urine contains 
little albumen. 

March 2nd- 3rd — 3 gr. through tube. Urine almost 
colorless. Little albumen. With NaOH hardly 
changed. Neither with muriatic acid. 



118 COAL TAR COLORS IN FOOD PRODUCTS. 

March 4:th-5th — 3 gr. through tube. Distinct albu- 
men. Urine colorless. Faeces colored blue. 

March 5th-6th — 5 gr. Urine colored weakly reddish 
violet, becomes colored fuchsine through HCl. 
Little albumen. 

March 6th-8th — Urine colorless. Little albumen. 
Animal lively. Did eat a great deal. 

March 9th-10th — Urine dirty bluish red. Is colored 
orange red with HCl. With NaOH bluish red. 
Dyeing of wool with the acidified urine succeeds. 

March llth-12th — 10 gr. through tube. Animal did 
eat. Urine and fsBces blue. 

March 12th-13th — Urine as above. Little albumen. 

March 13-14th — 20 gr. Quite some albumen. Ani- 
mal lively. Did eat. 

March 14th- 15th — Urine bluish. Distinct albumen. 

March 15th-16th — Urine almost colorless. Distinct 
albumen. 

March 18th-19th — Urine colorless. Little albumen. 

March 20tli-2 1st— Weight 26.62 kilos. 

A second dog (4.5 kilo) received daily during one 
month one gr. of Naphthol black through tube. Re- 
mained completely lively and retained its good ap- 
petite. 

b. Hypodermic Injection. 
Test HI. 

March 1st— Dog of 3200 gr. 

March 2nd-3rd — Urine colorless. No albumen. 

March 3rd-4th — Urine as above. 

March 4th-5th — 0.1 hypodermic in 10 ccm. lukewarm 



DISAZO COLORS. 119 

water injected under the skin of the back (right 
side). 

March 5th-6th — Urine scarce. Colorless. No albu- 
men. No abscess. 

March 6th-Yth — 0.1 hypodermic. Animal ate little. 

March Tth-8th — No abscess. Urine colorless. No 
albumen. Did not eat anything. 

March 8th-9th — Died during the night of 8th-9th. 
Weight 2550 gr. 

Dissection. — No abscesses. No hardening of the 
places where the injections were made. Under the 
skin near the places where the injections were made a 
great deal unchanged coloring matter. Free of micro- 
organisms. Gelatine plates which were inoculated 
with the coloring matter taken out of the injection 
places remained sterilized during nine days. Corpse 
not yet stiff. Very lean. Mucous membranes and 
muscles colored normal. Intestines very pale. Me- 
sentery considerably reddened. Liver, spleen, kid- 
neys, lungs strongly hypersemic. Nowheres exuda- 
tions. 

Test IV. 

March 9th-10th — Dog of 3860 gr. Animal was used 
before for other experiments. Very lean. 

March lOth-llth — Urine colorless. Little albumen. 

March llth-12th — 0.1 hypodermic in 10 ccm. water. 

March 12th-13 — No abscess. Animal miserable. 
Urine scarce. Almost colorless. With NaOH, 
acetic acid, and muriatic acid no change in color. 
Distinct albumen. 0.1 Hypodermic. 



120 COAL TAR COLORS IN FOOD PRODUCTS. 

March 13th-14th — 0.1 hypodermic. Urine colorless. 

No abscess. 
March 14th-16th — Urine colorless. Albumen very 

distinct. Animal did eat, but is very miserable. 
March 17tli-19th — No abscesses. Animal very lean. 

Distinct albumen. 
March 20th-21st— Ate a great deal. 3887 gr. 
March 25th — Animal very lean. Did eat. Is killed 

with prussic acid. 

Dissection. — The subcutaneous cellular tissue of the 
back where the injection was made is colored dark 
bluish red. The muscles show the same color. Liver 
and the other organs hyperaemic and enlarged. Eec- 
tum a little bluish red colored. Conjunctivae and 
mucous membranes of the mouth not colored. 

This coloring matter is harmless through the stom- 
ach but harmful in hypodermic injections. 

4. Congo. 
C32 H,o Ne Oe S, Na^ 

A red powder. The watery reddish solution yields: 

With muriatic acid, a blue precipitate which is 
hardly soluble even in hot w^ater. 

With acetic acid, as with muriatic acid. 

With liquor sodse, only in concentrated solution a 
reddish brown precipitate easily soluble in water. 

With ammoniacal copper solution, a gelatinous red 
precipitate, soluble in excess of water with red color. 

By dusting in concentrated sulphuric acid, same is 
colored blue. If diluted with water a blue precipi- 
tate is produced. Dyes cotton and wool red without 
corrosion. 



DISAZO COLORS. 121 

a. Stomachical Application. 
Test I.— Dog of 7300 gr. 

Dec. 14:th-17th — Traces of albumen. 

Dec. 18th — 2 gr. of congo in peptone through tube. 
Animal lively. Urine colored almost normal. 

Dec. 19th — 2 gr. of congo. Urine pale. Weakly alka- 
line. Traces of albumen. No sugar. 

Dec. 20th — 2 gr. congo. Urine colored faintly red. 
Not changed through acids. Yellow through 
NaOH. Little albumen. Hard faeces. 

Dec. 21st — 3 gr. congo. Dog lively. Solid faeces. 
Urine colored a little reddish. The dyeing of cot- 
ton in the urine not otherwise prepared succeeds 
very well. The red colored cotton is colored 
bluish through acids. Little albumen in the 
urine. 

Dec. 23rd-26th — Lively. Urine pale red. Contains 
a reddish sediment. (Congo !). 

Dec. 27th — 5 gr. of congo in peptone. Lively. Urine 
almost colorless. Weakly alkaline. Little albu- 
men. 

Dec. 28th — 10 gr. congo. Dyeing of cotton is suc- 
cessful. Little albumen in the urine. 

Dec. 30th — 10 gr. of congo. Animal ate little, but 
lively. Urine little colored. Weak alkaline. 
Little albumen. Sulphates present. Weight 
6980 gr. Decrease 320 gr. in 16 days. 

Dec. 31st — Lively. No injection. Soft pasty faeces. 
Temporarily discharged. 

Jan. 15 til — Animal lively. 



122 COAL TAR COLORS IN FOOD PRODUCTS. 

A second dog of 4.3 kilos received one gr. congo 
through tube daily for one month . The dog remained 
absolutely well. 

b. Hypodermic Injection. 

Test II.— Dog of 4970 gr. 

Jan. 4th — Urine contains traces of albumen. 

Jan. 5th — 0.25 gr. congo in 10 ccm. water hypoder- 
mically injected under the skin of the back, on 
the right side. 

Jan. 6th — Urine hardly colored. Almost free of al- 
bumen. 

Jan. 7th — 0.25 gr. hypodermically injected under the 
skin of the back, right side. Urine colorless. 
Alkaline. Little albumen. Animal seems weak. 

Jan. 8th — Ate little. Urine colorless. No abscess. 

Jan. 9th — Urine colorless. Ate little. 0.25 gr. un- 
der the skin of the back, left side. Abscess on 
the abdomen right side of the centre line. 

Jan. 10th — Ate little. Urine colorless. 0.25 gr. hy- 
podermically injected under the skin of the back, 
left side. Big abscess right of the linea alba. 

Jan. 11 — Animal very weak. Urine almost colorless. 
Contains little albumen. The big abscess on the 
right side of the abdomen is split. About 15 ccm. 
of a blood red liquid are extracted in which can 
be detected fat drops with the naked eye. The 
liquid curdles after 10 minutes. Shows after a 
proportionate diluting, stripes of Oxyhsemoglobine 
— ^but only very weak. Is colored intensely blue 
with acids. Consists, therefore, for the largest 
part of completely unchanged not resorbed congo. 



DISAZO COLORS. 123 

With the microscope can be observed fat drops, 
red blood particles, the latter partly in normal 
and partly in abnormal shapes, further, also, pus 
cells. Micro-organisms which, according to 
Gramm, can endure the coloring, were not found. 

Jan. 12th — Animal very weak and dejected. Weight 
4300 gr., showing a decrease of 670 gr. within 
eight days. Animal dejected and weak. 

Jan. 13th-14th — The abscess opened on Jan. 11th ex- 
pels voluntarily a red colored liquid in which is 
contained considerable congo coloring matter 
(bluing through acids). 

Jan. 15th — The unopened abscess on the left side 
seems to become resorbed. Temperature 39.5 
degrees in recto. 0.25 gr. hypodermic. 

Jan. 16 — Animal very miserable. Does not eat. In 
recto 39.5. Opened abscess seems to close up. 

Jan. 18 — Temperature 39.2. Miserable. Eats little. 

Jan. 22d — Ate something. Cranky and miserable. 
40.5 degrees in recto. 

Jan. 24th — Weak and cranky. Did eat. 

Jan. 29th — The one abscess opened voluntarily and 
expelled unchanged coloring matter as well as 
pus. Animal eats, but is very weak. 

Feb. 5th — Dog is lively again. Did eat. The ab- 
scesses on the abdomen were probably abscesses 
produced directly from the injection places. 

According to Tests I and II congo is harmless even 
in continued application through the stomach. The 
disturbances which appeared in hypodermic injection 
(Test III) are probably effected through the invasion 



124 COAL TAR COLORS IN FOOD PRODUCTS. 

of decay organism and would then have no direct con- 
nection with the coloring matter. 

6. Azo Blue. 

C34 H24 N4 O2 Nas. 

Black blue powder quite easily soluble in water with 
a reddish violet color. 

The watery solution yields: 

With muriatic acid, a reddish violet precipitate 
which is easily soluble in water and in alcohol. 

With liquor sodse, a cherry red solution. 

With concentrated sulphuric acid, a blue precipitate 
which is soluble in the excess of sulphuric acid with 
an indigo blue color. 

By dusting in concentrated sulphuric acid indigo 
blue solution is produced, which becomes cloudy upon 
addition of water, at the same time precipitating a 
violet colored sediment. This sediment is soluble in 
water with violet color. The solution of the color in 
concentrated sulphuric acid when boiling becomes 
brown colored under decomposition. 

With ammoniacal copper solution, a cherry colored 

precipitate is produced which is almost insoluble in 

water. 

a. Stomachical Application. 

Test I.— Dog of 8450 gr. 
Jan. 7th — Urine pale. Colorless. Little albumen. 
Jan. 8 th — Urine as on the 7 th. 2 gr. through tube in 

peptone. 
Jan. 9th — Dog lively. Did eat. Dark colored faeces. 

Urine colorless. With NaOH temporarily colored 

greenish. Albumen? 



DISAZO COLORS. 125 

Jan. 10th — 2 gr. through tube. Urine colorless or 
shining faintly violet. Strong alkaline. Little 
albumen. With NaOH or NHg temporarily 
greenish. Nothing characteristic with ferric 
chloride. 

Jan. 11th — 5 gr. through tube. Urine colorless. Lit- 
tle albumen. When boiling with concentrated 
muriatic acid (not with diluted acetic acid) it is 
colored remarkably bluish black and very dark. 
It yields to ether a bluish red colored matter. The 
distillate is free from phenol. 

Jan. 12th — 8 gr. azo blue. Urine a little bluish violet. 
Plentiful. Animal lively. Little albumen. Does 
not reduce alkaline copper solution. 

Jan 13th-14th — No injection. Urine colorless. 

Jan. 15th — 5 gr. azo blue. Urine colorless. 

Jan. 16th — Urine colorless. Little albumen. 

Jan. 18th — Urine colorless. Little albumen. 5 gr. 
of azo blue. 

Jan. -SOth — Urine colorless. Little albumen. Weight 
8490 gr. 

Another dog of 4. 7 kilos received during one month 
1.5 gr. azo blue through tube. The animal remained 
well and in good appetite. Albumen appeared very 
sparingly only in the urine. 

b. Hypodermic Injection. 

Test III.— Dog of 4600 gr. 

Jan. 26th-28th — Urine normal. 

Jan. 29th — 0.20 gr. in 10 ccra. water hypodermically 
injected. (Left half of the back.) 



126 COAL TAR COLORS IN FOOD PRODUCTS. 

Jan. 30th — Abscess commencing on left side. 0.20 
gr. in 10 ccm water hypodermic injection. (Right 
half of the back.) 

Jan. 31st — Abscess on the left half of the back was 
opened. It expels a violet gelatinous matter 
but only a few drops of blood. The expelled 
coloring material is unchanged azo blue. The 
pus contains a great many pus kernels and 
great many putrefaction bacilli. The urine is 
colorless. Little albumen. Weight 4580 gr. 

Feb. 3rd — Dog eats and is livelier. 

Feb. Tth — 0.20 gr. injected under the skin of the 
the abdomen with carefully sterilized syringe 
after the place of the injection was thoroughly 
disinfected. 

Feb. 10th — No abscess. Animal lively. 

Feb. 15th — No abscess. 

Feb. 24:th — Animal lively. No abscess. 

Azo blue is harmless through the stomach as well as 
in hypodermic injections. The disturbances in hypo- 
dermic injections could be traced to the invasion of 
putrefaction bacteria. 

6. Chrysamin R. 

C28 H20 N4 Oe Nag 

A brownish yellow powder soluble in water with a 
brown color. 

The watery solution yields: 

With muriatic acid, a gelatinous brown precipitate 
which is hardly soluble in water, easier soluble in 
alcohol with a brown color. 



DISAZO COLORS. 127 

With acetic acid, brown flakes. 

With liquor sodae, a gelatinous reddish brown sedi- 
ment which is soluble in water with a reddish brown 
color. 

With ammonia, a reddish brown solution. 

With ammoniacal copper solution, a gelatinous red 
brown coloring which it is very hard to dissolve in 
water. 

By dusting in concentrated sulphuric acid a reddish 
violet solution is produced, upon addition of water 
brownish flakes are precipitated. 

Dyes cotton yellow in the soap bath. 

a. Stomachical Application. 
Test I.— Dog of 9230 gr. 

Jan. 2nd — Urine colored normal. Alkaline. Very 
little albumen. Considerable sulphates. 

Jan. 3rd — 5 gr. chrysamin in peptone through tube. 
Faeces yellowish, thin. Urine alkaline, yellowish. 
Dyeing of cotton with urine successful. Very 
little albumen. 

Jan. 4th — 5 gr. chrysamin. 

Jan. 5th — Urine yellowish. With NaOH red. Diarr- 
hoea. Animal lively. Did eat. 

Jan. 6th-7th — Animal lively. Little diarrhoea. 
Urine almost colorless. Little albumen. Plenty 
of sulphates. Alkaline. 

Jan. 7th — 1 gr. chrysamin. Urine little colored. 
Contains distinct albumen. 

Jan. 8th — No injection. Urine little colored. A little 
albumen. 



128 COAL TAR COLORS IN FOOD PRODUCTS. 

Jan. 9th — 1 gr. chrysamin in peptone. Lively. 

Fseces yellowish. 
Jan. 10th — 2 gr. of chrysamin. Dog lively. Runs 

about freely all day. 
Jan. 11th — 2 gr. chrysamin. Animal lively. 
Jan. 12th — 3 gr. chrysamin. 
Jan. 13th — Animal lively. Did eat. 
Jan. 14th — Weight 9600 gr., therefore 370 gr. 

gained within 12 days. 
Jan. 15th — Lively. 3 gr. chrysamin. 
Jan. 16th-20 — Little albumen. Lively. Did eat. 

In Test II. an animal of 11.3 kilos received in the 
course of 10 days three doses each of 10 gr. coloring 
through the tube. The urine was colored yellowish 
and contained little albumen. The animal was lively 
even 14 days after the last application. 

b. Hypodermic Injection. 
Test III.— Dog of 3680 gr. 

Jan. 9th — Qrine colorless. Traces of albumen. 

Jan. 10th — 0.25 gr. chrysamin in 10 com luke-warm 
water hypodermically injected. Urine neutral. 
A little yellowish. Little albumen. 

Jan. 11th — Animal does not eat. No abscess. Dyeing 
of cotton not successful. 0.25 gr. hypodermic. 

Jan. 12th — Animal weak. No abscesses. Urine colored 
a little, also contains little albumen. 0.25 gr. 
hypodermic. 

Jan. 13th — Little albumen. 

Jan. 14th — Animal dejected. No injection. 2 ab- 
scesses on the back. 40 degrees in recto. 



CONCLUSIONS. 129 

Jan. 15th — 0.25 gr. hypodermic. Urine pale yellow. 

Distinct albumen. Cotton dyeing not successful. 
Jan. 16th — No injection. Cranky. 39.5 degrees. 

Eats little. An abscess on the back opened by 

itself and discharged a yellow liquid (Chrysamin). 
Jan. 17th — Animal cranky. 39.5 degrees in recto. 

Abscesses as on the 16th. 
Jan. 18th — Abscess discharges. Little color. 
Jan. 19th-21st — Temperature 39.5 degrees. Cranky. 

Ate little. A new abscess seems to form. 
Jan. 22nd— Eats little. 

The abscess split with the knife discharges about 20 
ccm of a gelatinous matter which has the color of the 
injected coloring and in which is found unchanged 
color. In the discharged matter bacteria could not be 
proven for a certainty. Such species which stood 
Gramm's method were positively not present. Great 
many fat drops, blood only in traces. 

Weight 3210 gr. 

The color is harmless through the stomach. The 
abscesses after hypodermic injection can possibly be 
traced back to invaded putrefaction organisms, 
although their existence could not be proven with cer- 
tainty. 

III. Conclusions. 

1. Among the twenty-three so far examined azo 
colors only two — namely, metanil yellow and orange 
II. — showed such effects through the stomach that 
they can be pronounced poisonous. The dosis lethalis 
for the dog consisted for Orange II. of less than 1 gr. 



130 COAL TAR COLORS IN FOOD PRODUCTS. 

per kilo, and for metanil yellow only 0.53 gr. per 
kilo. 

Of the other coloring matters, a few caused vomit- 
ing (Bismarck brown), diarrhoea (Fast brown, 
Chrysamin R.), and a great many of them albuminu- 
ria of a lighter degree. 

The appearances observed in hypodermic injection 
are doubtful. The produced abscesses were traced 
back in a few cases (for instance, azo blue) to the in- 
vasion of micro-organisms. Naphthol Black P., how- 
ever, works evidently poisonous in hypodermic injec- 
tions. 

It seems remarkable how slow in some cases 
the hypodermically injected watery color solutions 
were absorbed. Congo could be proven (in Test III.) 
even seven days after the injection, in large quanti- 
ties. The same was also observed in Chrysamin. 

2. The tests with the coloring materials from m- 
Nitraniline-f/^- Naphthol, p-Nitraniline+Schaeffer's 
Salt, p-Nitraniline-f Naphthion acid( = Orseille substi- 
tute) show that the addition of a nitro group into an 
azo color does not produce a poisonous color, as the 
experiments made with the nitro colors would lead us 
to expect. This harmlessness of the nitro group in 
the azo coloring, however, is not produced through 
the presence of a sulpho group, which dis-poisoning 
influence was also observed in the nitro colors. This 
conclusion has to be arrived at from the harmlessness 
of the metanitrazotin (m Nitraniline+/?-Naphthol), 
which contains no sulpho group and is non-poisonous 
in spite of the nitro group. 

3. That colors can be poisonous in spite of the 



CONCLUSIONS. 131 

presence of the sulpho group has been proven through 
the experiments with Orange II. (Sulfanil acid + 
/^-Naphthol), and with metanil yellow (out of m- 
Amidobenzolsulpho acid+Diphenylamine). 

4. The poisonousness of Orange II and of metanil 
yellow can be traced back to their constitution, as two 
other colors of known constitution, which are closely 
related to the constitution of the above, proved to be 
harmless. 

(a) The poisonous metanil yellow corresponds with 
the non-poisonous Diphenylamine Orange. As the fol- 
lowing formulas will show, the difference of the two 
materials is in the position of the sulpho group to the 
azo group. 

In Diphenylamine orange said groups are contained 
in para position, in metanil yellow, in meta position. 
The correctness of these formulas is proven by the fact 
that metanil yellow is produced through Diazotizing 
of Meta- Amidobenzolsulpho acid ; Diphenylamine Yel- 
low through Diazotizing of Para- Amidobenzolsulpho 
acid (Sulfanil acid). 

^ „ (1) SO3 Na ^ ^ (1) SO3 Na 

^^6^4(4) N = N— C6H4NHC6H5 ^^^\d) N = N— CsH^NHOeHs 
Non- poisonous. Poisonous. 

(6) With Orange II., which is poisonous, corre- 
sponds a second color, the non-poisonous Orange I. 

Both materials differ only through the position of 
the hydroxy 1 in the Naphthalin. 

In Orange I. hydroxyl has the a position, 
in Orange II. the ^ position. This results from the 
production of the colors which are produced in one 



132 COAL TAR COLORS IN FOOD PRODUCTS. 

case with the help of a Naphtol, in the other case 

with the help of /? Naphtol. 

(4) SO3 Na p „ (4) SO3 Na 

^6^4(i)N ^ N— CioH60H(a) ^6^X1)^ = N— CioHeOHd:^) 

Orange I. Orange II. 

(a-Naphthol Orange) (/i-Naphthol Orange) 

Non-poisonous. Poisonous. 

Other azo colors, which contain also the balance of 
/^-Naphthol, for instance, Sudan I., Neucoccin, Fast 
red B., Xylidin red and Azarin S., are absolutely 
non-poisonous. 

The dog urines, discharged after feeding and hypo- 
dermic injection of azo colors, were frequently 
normally colored, and contained the unchanged color- 
ing material only then when very large quantities of 
coloring material were embodied in the organism. A 
part of the fed colors is also found in the faeces, prin- 
cipally when the colors fed were not soluble. At 
any rate, however, a frequently complicated built 
color molecule is divided in the animal body and 
changed into uncolored products. I have never been 
successful so far to produce colored materials out of 
urines discharged colorless after feeding with azo 
colors, which could have closer connection with the 
color molecule fed previously. 



In order to show to what degree some of the coal 
tar colors are harmless, I have made physiological 
tests with a few of those colors which are especially 
and frequently used for food products. 

Although it was impossible to establish the exact 
pedigree and thereby the exact age of the animals 



TARTRAZINE. 133 

employed, I am confident that none of the animals, 
with the exception of the ^'uinea pigs, were older than 
two months. (My opinion was shared by people who 
make the handling of animals their business, and 
therefore ought to be somewhat competent judges.) 
I preferred to employ these young animals, as ex- 
perience in various previous tests had taught me that 
a fully developed and matured animal will frequently 
be able to partake of, comparatively speaking, large 
doses without any apparent bad effects, which doses, 
however, sufficed to severely injure, frequently even 
to kill, very young animals of the same class. 



Tartrazine.^ 
COOH 

C=N\ / s^ 



li__NH-<^ 




SO«.Na 



resp 



COOH 
HC— CO-^ ^ ^ 



SO.Na 




N=N-< V-SOaNa 



Disodium salt of 1-p-sulphoxylphenyl : 3-carboxyl- 
4-p-sulphoxylphenyl-hydrazono-5-pyrazolon. 

Orange yellow powder readily soluble in water 



*G. Schultz & P. Julius Tabellarische Uebersicht. 



134 COAL TAR COLORS IN FOOD PRODUCTS. 

with a greenish to gold yellow color. The solution in 
water yields: 

With muriatic acid, no change. 

With liquor sodse, a more reddish color. 

Tartrazine dissolved in sulphuric acid yields an 
orange yellow solution which is turned yellow upon 
diluting with water. 

Test I. 

Male Dog of 5445 gr., presumably not older than 
two months. 

When received, somewhat sullen. Did not display 
much appetite during first day (treatment commenced 
day after received). Suffered of mild diarrhoea. Eyes 
rather dull. Otherwise lively and seemed in fair con- 
dition. 

May ITth, 10 a. m. — Injection 0.20 gr. through tube. 
The color had been previously dissolved in 20 cc. 
water and a little peptone had been added. Dog 
ate well about noontime. Was lively and more 
playful. Mild diarrhoea continued; in fact, seemed 
to have increased somewhat. 

May 18th, 10 a. m. — No injection. Dog lively. Pasty 
faeces. Good appetite. Weight 5405 gr., a loss 
of 40 gr. for which I think diarrhoea had to ac- 
count. 

May 19th, 10 A. m. — Injection 0.20 gr. dissolved same 
as above, through tube. Dog kept lively through- 
out the day. Displayed good appetite. Solid 
faeces. 



CURCUMIN. 135 

May 20th, 10 A. M. — No injection. Dog lively. Good 

appetite. 
May 21st, 10 a. m. — Injection 0.20 gr. Dog lively. 

Appetite as usual. 
May 22 nd — No observation on account of Sunday. 
May 23rd, 10 a. m. — Injection 0.20 gr. dissolved same 

as above. Dog appeared somewhat sullen but 

displayed good appetite. Suffered of mild 

diarrhoea. 
May 24th, 10 A. M. — No injection. Dog is livelier. 

Appetite fair. Diarrhoea continues but seems to 

be somewhat decreased. 
May 2oth, 10 A. m. — Injection 0.20 gr. dissolved same 

as before. Dog lively. Very playful. Appetite 

as usual. 
May 26th, 10 a. m. — No injection. Appetite as usual. 

Solid faeces. Lively. 
May 27th, 10 A. M. — Injection 0.20 gr. in solution same 

as before. Appetite as usual. Very lively and 

playful. Pasty fseces. 
May 28th, 10 A. M. — No injection. Dog lively. Good 

appetite. Weight 5560 gr. or a gain of 115 gr. 

in total weight. 

Test discontinued. 

CURCUMIN.* 

Is the sodium salt of Sulphanilacid-azodyphenylamin- 
sulphoacid. 

Orange yellow powder, frequently dark brown 
powder which graduUy bleaches into a golden to 

*G. Schultz & P. Julius Tabellarische Uebersicht. 



136 COAL TAR COLORS IN FOOD PRODUCTS. 

orange yellow. Readily soluble in water with yellow 
color. 

The watery solution yields : 

With muriatic acid, violet-red solution. 
With little liquor sodse, no change. 
With much liquor sodae, violet-red. 

Soluble in sulphuric acid with bluish red color, if 
diluted with water fuchsine red. 

Test II. 
Very young male rabbit of 0.250 ko. 

Animal seemed in good condition when received, 
was lively and displayed considerable appetite (May 
16th). 

I dissolved the Curcumin applied to the rabbit at 
the rate of 1 gr. in 25 cc. of water and added some 
peptone to each dose. The injections were made by 
means of tube precisely 10 a. m., no food was given to 
the animal until 10:30 a. m., and previous to same 
the weight was taken. 

May 17th — Injection of 2cc. solution as above. Animal 

lively. Weight 0.250 ko. Eats well. 
May 18th — No injection. Weight 0.255 ko. Eats 

well. 
May 19th — Injection of 2 cc. solution. Animal lively. 

W^eight 0,256 ko. Eats well. 
May 20th — No injection. Weight 0.253 ko. Animal 

lively. Great desire to eat. 



CARMOISIN. 137 

May 21st — Injection of 2 cc. solution. Animal lively. 

Weight 0.261 ko. Desire to eat not diminished. 
May 22nd — No observation. 
May 23d — Injection of 2 cc. solution. Animal lively. 

Weight 0.260 ko. Great desire to eat. 
May 24th — No injection. Otherwise no change from 

day before. 
May 25th — Injection of 2 cc. solation. Animal lively. 

Weight, 0.264 ko. Appetite normal. 
May 26th — No injection. Animal lively. Weight 

0.266 ko. Did not eat as much as usual. 
May 27th — Injection of 2 cc. solution. Animal very 

lively. Weight 0.270 ko. Considerably increased 

appetite. 
May 28th — No injection. Animal lively. Weight 

0.273 ko. Appetite as usual. Gain in total 

weight 23 gr. Discontinued. 

Carmoisin.* 
OH 




SOgNa 

Sodium salt of Naphtionacid - azo - 1 - naphthol-4- 
sulpho acid. 

Brown powder soluble in water with fuchsine red 
color. 



*G. Schultz & P. Julius Tabellarische Uebersiclit. 



138 COAL TAR COLORS IN FOOD PRODUCTS. 

The watery solution yields : 

With muriatic acid, dark red precipitate. 

With liquor sodse, somewhat more yellowish. 
. In sulphuric acid, violet solution, upon addi- 
tion of water fuchsine red. 

Test III. 

Guinea pig (male), age unknown, fully developed, 
weight 0.518 ko. Was very timid in new surround- 
ings, refused food at first, but later in the day com- 
menced to eat a little (May 16th). 

The color applied to this animal was dissolved in 
proportion of 1 gr. in 32 cc. water. Each injection 
consisted of 4 cc. of above solution through tube. 
Injections were made at 10 A. M., then the weight of 
the animal was taken and at 10:30 A. M. the animal 
received its food. 
May 17th — Injection. Animal timid. Weight 0.512 

ko. Appetite somewhat increased. 
May 18th — No injection. Animal less timid. Weight 

0.515 ko. Appetite increasing. 
May 19th — Injection. Animal quite lively. Weight 

0.515 ko. Appetite very good. 
May 20th — No injection. Animal lively. Weight 

0.520 ko. Appetite considerable. 
May 21st — Injection. Animal sullen. Weight 0.516 

ko. Appetite good. Seems very thirsty. 
May 22nd — No observation. 
May 23rd — Injection. Animal lively. Weight 0.515 

ko. Appetite considerable. Drinks less. 
May 24th — No injection. Otherwise same as May 

23rd. Weight 0.519 ko. 



PONCEAU 2 R. 139 

May 25th — Injection. Animal very lively. Weight 

05.16 ko. Appetite good. 
May 26th — No injection. Otherwise same as May 

25th. 
May 27th — Injection. Animal lively. Weight 0.516 

ko. Appetite good. 
May 28th — No injection. Animal lively. Weight 

0.517 ko. Appetite considerable. Loss in total 

weight 1 gr. Discontinued. 

Ponceau 2 R.* 

N-N-CeH3(CH3)2 
.OH 



^ 




Sodium salt of Xylidin-azo-2-naphthol-3,6-disulpho 
acid. 

Brownish red powder, readily soluble in water with 
yellowish red color. 

The watery solution yields : 

With muriatic acid, no change. 
With liquor sodse, darker and more yellowish 
colored. 
In sulphuric acid, cherry-red solution; upon addition 
of water reddish yellow solution. 

Test IV. 
Guinea pig (female). Age unknown, fully devel- 
oped. Weight 0.403 ko. Was sullen and timid 



'G. Schultz & P, Julius Tabellarische Uebersicht. 



140 COAL TAR COLORS IN FOOD PRODUCTS. 

when received. Ate little ; drank some milk. (May 
16th.) 

The color fed to the animal was dissolved in water 
in proportion of 1 gr. to 32 cc. of water. Each dose 
applied consisted of 4cc. of above solution. Through 
tube. The injections were made at 10 A. M., then the 
weight was taken and at 10.30 the animal received 
its food. 

May lY — Injection. Animal sullen. Weight 0.403 

ko. Little appetite. Drank some milk. 
May 18 — No injection. Animal less sullen. Weight 

0.398 ko. Appetite increasing. Drinks milk 

with great desire. 
May 19th — Injection. Animal less sullen. Weight 

0.400 ko. Appetite increasing. Hardly touches 

the milk. 
May 20th — No injection. Animal lively. Weight 

0.402 ko. Good appetite. 
May 21st — Injection. Animal lively. Weight 0.403 

Ko. Good appetite. 
May 22nd — No observation. 
May 23rd — Injection. Animal lively. Weight 0.402 

ko. Considerable appetite. 
May 24 — No injection. Animal less lively. Weight 

0,404 ko. Less appetite. Drinks quite some 

milk. 
May 25th — Injection. Animal somewhat sullen and 

timid. Weight 0.400 ko. Eats little. 
May 26th — No injection. Animal quite lively. 

Weight 0.403 ko. Good appetite. 



RHODAMIN B. 



141 



May 27th — Injection. Animal lively. Weight 0.404 
ko. Good appetite. 

May 28th — No injection. Animal lively. Weight 
scant 0.404 ko. Good desire to eat. No appre- 
ciable change in total weight. Discontinued. 



Rhodamin B.^ 



CI 




(Q H^)^ \/\/^\/K/^ (^2 H5V, 



\AcA/ 



CO. OH 



V 

Phtalein of Diathylmetamidophenol (basic chlorhy- 
drate). 

Eeddish to reddish-violet powder, soluble in water 
with bluish red color, diluted solutions of bluish pink 
color, fluoresce brownish. Readily soluble in alcohol 
with color same as watery solution, same fluorescence. 
Fluorescence disappears upon heating, reappears when 
cooled off. 



The aqueous solution yields : 

With muriatic acid, gradual precipitation of 
green crystals of the chlorhydrate ; continued 



*G. Schiiltz & p. Julius Tabellarische Uebersicht. 



142 COAL TAR COLORS IN FOOD PRODUCTS. 

addition of muriatic acid produces scarlet color 
turning bluish red upon addition of water. 

With liquor sodse, if in small proportion, no 
change in the cold solution; if heated, precipi- 
tation of pink flakes. Addition of large pro- 
portion of liquor sodse produces in the cold 
solution a precipitation of pink flakes, which 
are soluble in ether and benzol without color. 
When heated with liquor sodse odor of dime- 
thylamine. 

In sulphuric acid, yellowish brown solution 
with production of muriatic acid. Solution 
fluoresces strongly greenish. Upon addition of 
water, the color of the solution changes first to 
scarlet and gradually to bluish red. 

Test V. 

Very young rabbit (female) of 0.236 ko. 

Animal was lively when received, seemed in good 
condition, displayed but little appetite. (May 16th.) 

The color fed to the animal was dissolved in water 
in the proportion of 1 gr. to 25 cc. water. Each injec- 
tion consisted of 2 cc. of solution with a little peptone 
through tube. The animal received one injection every 
other day at 10 A. M. Then the weight was ascer- 
tained and at 10.30 A. m. the animal received its fcod. 

The test covered the period Irom May I7th to May 
28th inclusive, when the test was discontinued. 

During the whole period the animal seemed to be 
perfectly at ease, was lively, displayed good appetite 
and gained steadily, so that it would be superfluous 
to record each single day. The weight of the animal 



NAPHTHOL YELLOW S. 143 

on May 28th was 0.253 ko. or a total gain of 17 gr. 
The test was then discontinued. 

Naphthol Yellow S.* 
OK 



^^^^\y\y\y^^^ 




NOa 

Potassium of sodium salt of 2.4-Dinitro-l-naphtol- 
7-sulpho acid. 

Yellow or orange yellow powder, burns with yel- 
low color, discharging at the same time sparks. 
Keadily soluble in water with yellow color. 
The aqueous solution yields : 

With muriatic acid, no precipitate, solution 
becomes considerably lighter in color, event- 
ually fades out entirely. 

With KOH, even in very weak solutions^ 
flaky precipitate. 

With liquor sodae, no change. 
In sulphuric acid yellow solution ; upon ad- 
dition of water becomes lighter, but no pre- 
cipitate. 

Test VI. 

Male dog of 5.602 Ko. About two months old (?). 
Same dog as used in Test I. 

When test commenced dog was lively, good appe- 
tite, drank normally, faeces normal. 



*G. Schultz & p. Julius Tabellarische Uebersicht. 



144 COAL TAR COLORS IN FOOD PRODUCTS. 

The color fed to the dog was dissolved in water in 
proportion of 1 gr. to 20 cc. water. The dose ap- 
plied consisted of 4 cc. of above solution with a little 
peptone. Through tube. 

The dog received the above dose every other day 
commencing June 1st and terminating June 14th. 
During the whole period the dog was uniformly 
lively and playful. The animal did not seem to dis- 
like the color at all, but was always ready to receive 
the color without any attempt to avoid same. The 
appetite remained about uniformly good. The dog 
drank much milk and at the end of the test was in 
excellent condition. The weight taken daily showed 
a steady increase of from 2 to 6 gr. Weight on June 
14th 5.661 gr. or a total increase of 59 gr. The test 
was then discontinued . The earlier part of July the 
dog was still in excellent condition and had gained 
considerably. 

Acid Green S. F.* 



CoHp 




SO,Na 



Sodium salt of diathyl-dibenzyldiamidotriphenylcar- 
binoltrisulpho acid. 

*G. Schultz & p. Julius Tabellarische Uebersicht. 



ACID GREEN S. F. 145 

Green powder soluble in water with green color. 
Soluble in alcohol. 

Aqueous solution yields : 

With muriatic acid, yellowish brown color. 
With liquor sodse, discoloration and dirty 
violet clouding. 

With barium chloride, no precipitate. 
With picric acid, no precipitate. 

In sulphuric acid, yellow solution which turns 
gradually green upon addition of water. 

Test VII. 

Male guinea pig, fully developed, age unknown. 

Animal seemed in excellent condition when test 
began. Same animal as used in Test III. Displayed 
good appetite before test commenced. Weight 0.521 
ko. (May 31st.) 

The color fed to this animal was dissolved in pro- 
portion of 1 gr. in 32 cc. water. Each injection con- 
sisted of 4cc. of above solution. Through tube. In- 
jections were made at 10 A. M., then the weight was 
taken and at 10: 30 A. M. the animal received its food. 
The animal received injection as described every other 
day commencing with June 1st and intended to cover 
the period of two weeks, but unfortunately on June 
10th the animal met with an accident by falling out 
of its cage and had to be killed. 

During the period in which the tests were made, 
that is, from June 1st to June 10th, the animal kept 
very lively and in good spirits. Had always consid- 
erable desire to eat, in fact, at times the appetite 



146 COAL TAR COLORS IN FOOD PRODUCTS. 



seemed enormous for the size of the animal. Drank 
little milk twice a day, but not in excess. The weight 
continually varied between 0.521 and 0.519 ko. The 
last time the animal was weighed it showed 0.520 
ko. As there was absolutely nothing irregular or 
abnormal observed during the whole test, there is no 
need of reporting or of specifying the result of each 
day. 

Soluble Blue.* 
• (Wasserblau.) 
CH, 



NaOaS.CgH^.HN, 



V^ 




NH.C«H<S05Na 



A 



X 



H.C,H,SO, 
I 



Sodium salts, ammonium salts, or calcium salts of 
triphenylrosanilin-and tryphenyl pararosanilintrisul- 
pho acids. 

Blue shining ^^' powder, soluble in water with blue 
color, but very little soluble in alcohol, 

Aqueous solution yields: — 



*G. Schultz & P. Julius Tabellarische Uebersicht. 



SOLUBLE BLUE. 147 

With muriatic acid, no change in color. 
Partly blue precipitate. 

With liquor sodse, brownish red solution. 
In sulphuric acid, dark reddish yellow. Upon addi- 
tion of water blue solution and blue precipitate. 

Test VIII. 

Guinea pig (female), age unknown but fully devel- 
oped. Weight before test commenced 0.405 ko. 

Animal lively. Good desire to eat. Animal seems 
in very good condition. Same animal as used in 
Test IV. 

The soluble blue fed to the animal was dissolved in 
water in proportion of 1 gr. to 32 cc. water. Of this 
solution 4 cc. were uniformly taken as a dose, which 
was applied every other day through tube. Injec- 
tions, as usual, were made at 10 A. M., then the 
weight was taken, and at 10:30 A. M. the animal re- 
ceived its food. 

The test commenced on June 1st (first application 
of color), the last application was made on June 13th, 
and the last observation taken June 14th. Through- 
out this time the animal appeared to be in good health, 
was lively and possessed considerable appetite, espec- 
ially was always desirous of drinking milk. Nothing 
irregular or disturbing whatsoever was observed dur- 
ing the whole period. The animal seemed to be per- 
fectly at ease and no change of any account was to be 
noted. The weight gradually rose to 0.408 ko., 
this being the weight taken on June 14th, when the 
observation was discontinued. 



148 COAL TAR COLORS IN FOOD PRODUCTS 

Naphthol Eed S. ^ 

N = N-C,oH«-S03Na 
OH 



.Na 




Na O, S^^^'^^'^^-^SO 



Sodium salt of Naphthion-acid-azo-2-naphtol-3-6- 
disulpho acid. 

Reddish brown powder. Readily soluble in water 
with fuchsine red color. Very little soluble in alcohol. 
Aqueous solution yields : — 

With muriatic acid, no change. 
With liquor sodae, solution becomes darker. 
In sulphuric acid, violet solution ; upon addition of 
water bluish violet . 

Test IX. 

Very young male rabbit. Same animal as used in 
Test II. 

Animal was in good condition when the test com- 
menced. Appetite fair. Weight 282 ko. 

The color fed to the rabbit was dissolved in water 
in proportion of 1 gr. in 25 cc. water. The dose ap- 
plied consisted of 2 cc. of above solution with a little 
peptone. The injections were made at 10 A. M., 
through tube, then the weight was ascertained and at 
10 : 30 A. M. the animal received its food. 



*G. Schultz & P. Julius Tabellarische Uebersicht. 



NAPHTHOL RED S. 149 

June 1st — Injection. Animal lively. Weight 0.283 

ko. Good appetite. 
June 2nd — No injection. Animal less lively. Weight 

0.281 ko. Appetite decreased. 
June 3rd — Injection. Weight 0.270 ko. Other- 
wise same as on June 2d. 
June 4:th — No injection. Animal livelier. Weight 

0.282 ko. Appetite increasing. 
June 5th — No observation. 
June 6th — Injection. Animal lively. Weight 0.281 

ko. Considerable appetite. 
June Tth — No injection. Animal lively. Weight 

0.283 ko. Appetite good. 
June 8th — Injection. Animal lively. Weight 0.286 

ko. Appetite as usual. 
June 9th — No injection. Animal lively. Weight 

0.285 ko. Appetite good. 
June 10th — Injection. Animal lively. Weight 0.287 

ko. Appetite good. 
June 11th — No injection. Animal lively. Weight 

0.289 ko. Appetite good. 
After feeding the animal in the afternoon it was 
caught between the doors of the cage when closing 
same, and as the animal seemed to suffer much pain 
it was killed. During the duration of the test the 
animal seemed perfectly at ease and gained 7 gr. 
in total weight. The apparent indisposition of the 
first days was of no great consequence. 

Owing to the number of coal tar colors already in 
existence and especially also considering the fact that 
their number increases very rapidly by new inven- 
tions, etc. , it would be almost impossible to subject 



150 COAL TAR COLORS IN FOOD PRODUCTS. 

everyone of them to similar tests, But this is, ac- 
cording to my opinion, not at all necessary, as by far 
the greatest number of these colors are never used for 
coloring of food products, but are solely employed for 
dyeing purposes in the various industries. Although 
it would be possible to draw quite reliable conclusions 
as to the advisability of employing certain colors for 
food products on the basis of their chemical constitu- 
ency, the mode of their manufacture and of the in- 
gredients used in same, nevertheless I think that the 
by far safest way would be on the one side to force 
the dealers of colors intended for food products to sell 
only such colors, with which exhaustive and careful 
physiological tests have been made by experienced and 
especially impartial and thoroughly reliable people, 
thereby establishing their harmlessness beyond a 
doubt. On the other hand the manufacturers and 
canners of food products of any description should be 
forced to purchase and use only such colors of which 
they are sure that they have been submitted to such 
careful tests as described before and through same 
have been found to be harmless. 



I^OV 14 1904 













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